JP3107045B2 - Method for producing multi-element mixed crystal and semiconductor device - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a multi-element mixed crystal used for a semiconductor device or the like. Also,
The present invention relates to a semiconductor element and an optical recording device using a multi-element mixed crystal.

[0002]

2. Description of the Related Art In the conventional production of a multi-element mixed crystal such as ZnSeTe or ZnSSe, a molecular beam produced by heating each material is used to control the composition. For example, Japanese Patent Application Laid-Open No. 9-293737 discloses a crystal growth method using a molecular beam obtained by heating and evaporating a solid of mixed crystal constituent elements. Japanese Patent Application Laid-Open No. 6-316486 discloses a crystal growth method using a molecular beam obtained by evaporating a compound by heating. Also, Applied Physics Letters, Volume 63, 1
In 993, p. 2935, a method is disclosed in which a solid is heated to thermally dissociate evaporated molecules for the growth of a mixed crystal containing only one group 6 element.

[0003]

However, in the above-mentioned prior art, the evaporated Se molecules are composed of a large number of atoms such as six or eight. Since a mixed crystal containing two kinds of Group 6 elements, such as ZnSeTe and ZnSSe, is produced using a molecular beam composed of such polyatomic molecules, a region (cluster) in which Se gathers in an island shape at an atomic level is formed. Would. For this reason, there have been problems in that the fluctuation of the composition is large, the electric resistance is large, the thermal resistance is large, and the emission and absorption spectrum widths are wide. In addition, there is a problem that the immiscibility is increased by the cluster, the temperature range in which a mixed crystal can be produced is narrow, and the production is difficult.

Further, when nitrogen is added to a mixed crystal containing Se as a p-type impurity, the nitrogen is locally incorporated in the cluster region on the growth surface because the nitrogen is less incorporated in the cluster region and the nitrogen is increased outside the cluster region. Will be added to Locally added nitrogen has a problem that a deep acceptor level is easily formed, and an increase in the amount of added nitrogen causes an increase in electric resistance.

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a multi-element mixed crystal having a small composition modulation with good reproducibility, and a light having a low electric resistance and a low operating voltage, and an optical recording apparatus having a high electric element and a high yield. .

[0006]

According to the present invention, there is provided a method for producing a multicomponent mixed crystal, comprising the steps of: evaporating antimony polyatomic molecules in a mixed crystal film containing antimony and a Group 5 element other than antimony; Decomposing the polyatomic molecule of antimony to produce a molecule having a small number of atoms; evaporating a polyatomic molecule of a group V element other than the antimony; Decomposing to produce a molecule having a small number of atoms; and producing the mixed crystal using the molecule having a small number of atoms of the antimony and the molecule having a small number of atoms of a Group 5 element other than the antimony as raw materials. It is characterized by the following.

In a mixed crystal film containing nitrogen and a group V element other than nitrogen, a step of evaporating a polyatomic molecule of the group V element other than nitrogen is provided. The method includes the steps of decomposing atomic molecules to produce a molecule having a small number of atoms, and producing the mixed crystal using the molecule having a small number of atoms as a raw material.

At this time, the method may include a step of exciting a nitrogen molecule or a nitrogen compound to form an excited molecule or an excited atom, and a step of manufacturing the mixed crystal using the excited molecule or the excited atom as a raw material.

In a mixed crystal film containing oxygen and a group 6 element other than oxygen, a step of evaporating a polyatomic molecule of the group 6 element other than oxygen is performed. The method includes the steps of decomposing atomic molecules to produce a molecule having a small number of atoms, and producing the mixed crystal using the molecule having a small number of atoms as a raw material.

At this time, the method may include a step of exciting an oxygen molecule or an oxygen compound to produce an excited molecule or an excited atom, and a step of manufacturing the mixed crystal using the excited molecule or the excited atom as a raw material.

In a mixed crystal film containing sulfur and selenium, a step of evaporating polyatomic molecules of sulfur, a step of decomposing the polyatomic molecules of sulfur to produce a molecule having a small number of atoms, Evaporating the polyatomic molecule of selenium, decomposing the polyatomic molecule of selenium to produce a molecule having a small number of atoms, and preparing the molecule having a small number of atoms of the sulfur and the molecule having a small number of atoms of the selenium. And producing the mixed crystal using the above as a raw material.

In a mixed crystal film containing sulfur and tellurium, a step of evaporating polyatomic molecules of sulfur, a step of decomposing the polyatomic molecules of sulfur to produce a molecule having a small number of atoms, Producing the mixed crystal using a molecule having a small number of sulfur atoms as a raw material.

In a mixed crystal film containing selenium and tellurium, a step of evaporating polyatomic molecules of selenium; a step of decomposing the polyatomic molecules of selenium to produce a molecule having a small number of atoms; Producing the mixed crystal using a molecule having a small number of atoms of selenium as a raw material.

A step of evaporating the tellurium polyatomic molecule; a step of decomposing the tellurium polyatomic molecule to produce a molecule having a small number of atoms; And manufacturing the same.

In the step of manufacturing the mixed crystal,
Irradiating nitrogen plasma at the same time to add nitrogen.

The mixed crystal is a BeMgSSe mixed crystal lattice-matched to GaP, a BeMgSe lattice mixed to ZnS.
It may be a Se mixed crystal, a MgZnSSe mixed crystal lattice-matched to GaAs, or a MgZnSSe mixed crystal lattice-matched to ZnSe.

The mixed crystal is BeZnSTe mixed crystal lattice-matched to GaP, BeZnS lattice-matched to ZnS.
Te mixed crystal, MgZnSTe mixed crystal lattice matched to GaAs, MgZnSTe mixed crystal lattice matched to InP, InA
MgZnSTe mixed crystal lattice matched to s, MgZnSTe mixed crystal lattice matched to GaSb, MgZnSTe mixed crystal lattice matched to ZnSe, MgZnS lattice matched to CdS
Te mixed crystal, MgZnSTe mixed crystal lattice-matched to CdSe, MgZnSTe mixed crystal lattice-matched to ZnTe, In
MgCdSTe mixed crystal lattice-matched to P, MgCdSTe mixed crystal lattice-matched to InAs, MgCdSTe mixed crystal lattice-matched to GaSb, MgCdS lattice-matched to CdS
Te mixed crystal, MgCdSTe mixed crystal lattice-matched to CdSe, or MgCdSTe mixed crystal lattice-matched to ZnTe may be used.

The mixed crystal is a BeZnSeTe mixed crystal lattice-matched to GaAs, and a BeZnSeTe mixed crystal is lattice-matched to ZnSe.
ZnSeTe mixed crystal, MgZnSe lattice matched to InP
Te mixed crystal, MgZnSeTe mixed crystal lattice-matched to InAs, MgZnSeTe mixed crystal lattice-matched to GaSb, C
MgZnSeTe mixed crystal lattice matched to dS, MgZnSeTe mixed crystal lattice matched to CdSe, MgZnSeTe mixed crystal lattice matched to ZnTe, MgCdSeTe mixed crystal lattice matched to InAs, MgC lattice matched to GaSb
dSeTe mixed crystal, MgCdSe lattice-matched to CdSe
Te mixed crystal or MgCdSeT lattice-matched to ZnTe
e may be a mixed crystal.

In addition, 2 containing only selenium as a Group 6 element
In forming a film of a Group 6 semiconductor mixed crystal, a step of converting nitrogen into plasma, a step of evaporating polyatomic molecules of selenium, and a step of decomposing the polyatomic molecules of selenium to produce molecules having a small number of atoms. The above-mentioned 2-, wherein nitrogen is added using the nitrogen plasma and the molecule having a small number of atoms of selenium as raw materials.
Manufacturing a Group 6 semiconductor mixed crystal.

The Group 2-6 semiconductor mixed crystal is GaAs.
BeMgZnSe mixed crystal lattice matched to s, BeMgZnSe mixed crystal lattice matched to ZnSe, MgZnCdSe mixed crystal lattice matched to InP, or M lattice matched to CdS
gZnCdSe mixed crystal may be used.

Further, the polyatomic molecules can be decomposed or excited by any of heating, electron beam irradiation, light irradiation, ion irradiation, and plasma. Further, the multi-element mixed crystal can be manufactured in a vacuum. The method may further include the step of fabricating the mixed crystal at a temperature at which the multiple mixed crystal becomes immiscible in a thermal equilibrium state.

The optical semiconductor device of the present invention uses a multi-element mixed crystal film having no composition fluctuation. The electronic semiconductor element of the present invention uses a multi-element mixed crystal film without composition fluctuation.

[0023]

Next, the present invention will be described in detail with reference to the drawings.

[Embodiment 1] FIG. 1 is a schematic view of a manufacturing apparatus for explaining a first embodiment of the present invention, and FIG.
FIG. 2B is a conceptual diagram for explaining a manufacturing method, and FIG.
Is a conceptual diagram for explaining a conventional technique.

The step of forming a Group III-V semiconductor mixed crystal 12 containing antimony and a Group V element other than antimony on a substrate 11 in a vacuum or atmosphere gas will be described. Antimony (S
b) heating 13 to produce Sb polyatomic molecules 28; Since antimony 13 is a stable molecule consisting of 4 atoms,
Mainly Sb ₄ is formed. The Sb polyatomic molecule 28 is decomposed by heating or the like in the dissociation chamber 14 to reduce the number of atoms in one molecule. For example the production of Sb ₂ 22 consisting of atomic Sb21 or 2 atoms.

At the same time, the group 5 element 15 is heated to produce a group 5 polyatomic molecule 29. Group V element 15 easily forms a polyatomic molecule, and P ₄ and As ₄ are formed. The group V polyatomic molecule 29 is decomposed by heating or the like in the dissociation chamber 16 to reduce the number of atoms in one molecule. For example, a group 5 atom 23 composed of one atom and a group 5 diatomic molecule 24 composed of two atoms are manufactured. Further, the group III element 17 is heated and evaporated. Group 3 elements do not form polyatomic molecules, and are group 3 atoms that are monoatomic.
Evaporate as 5.

Sb21, Sb having a small number of atoms in one molecule
_A mixed crystal 12 is produced by simultaneously irradiating the substrate 11 with 22 group 5, group 23 atoms, group 5 group 2 atom molecules 24 and group 3 atoms 25. For the substrate 11, a semiconductor such as GaAs, Si, or CdS, sapphire, glass, or the like can be used. By controlling the material and temperature of the substrate 11, a mixed crystal 12 having a uniform crystal orientation or an amorphous mixed crystal 12 can be obtained. The surface of the mixed crystal 12 thus manufactured is shown in FIG.
(A). Since antimony having a small number of atoms in one molecule and a group V molecule are used, Sb26
And the group V atoms 27 are uniformly mixed, and the mixed crystal 12 with less composition fluctuation is obtained. In contrast, the Sb polyatomic molecule 28
Mixed crystal 12 using group 5 polyatomic molecule 29 and group 3 atom 25
When the mixed crystal 1 was produced, as shown in FIG.
Since a region where Sb 26 is gathered and a region where group V atoms 27 are gathered are formed on the two surfaces, a mixed crystal having a very large composition fluctuation is formed.

As shown in FIG. 2A, in the mixed crystal 12 having a small composition fluctuation, the electric resistance and the thermal resistance are reduced, and the characteristics are excellent when used in a semiconductor device. Further, the forbidden band width becomes constant, and an optical device having a narrow emission spectrum can be obtained. In the mixed crystal 12 having a large composition fluctuation as shown in FIG. 2B, since the potential for carriers is not periodic, a phenomenon called Anderson localization is likely to occur, and an increase in electric resistance and thermal resistance.
Characteristics that are inconvenient for ordinary electric elements, such as broadening of the emission spectrum, become stronger. Such a composition fluctuation can be suppressed remarkably when both Sb polyatomic molecules 28 and Group V polyatomic molecules 29 are decomposed, as compared to when both are decomposed.

In this embodiment, two types of 5
Manufactured a 3-5 group semiconductor including a group, but is not limited to this.
A group 3-5 semiconductor including three or more types of group 5 may be manufactured. In addition, other mixed crystals such as chalcopyrite may be manufactured without being limited to the group 3-5 semiconductor.

In this embodiment, the polyatomic molecules are decomposed by heat in the dissociation chamber. However, the present invention is not limited to this, and the polyatomic molecules may be decomposed by other methods such as electron irradiation or light irradiation. In addition, InP, GaAs,
A group V molecule having a small number of atoms may be produced by heating and evaporating a compound having a high decomposition temperature such as InSb.

[Second Embodiment] FIG. 3 is a conceptual diagram for explaining a second embodiment of the present invention. A step of forming a group III-V semiconductor mixed crystal 302 containing nitrogen and a group V element other than nitrogen on the substrate 301 in a vacuum or atmosphere gas will be described. A gaseous nitrogen compound 305 such as a nitrogen molecule is introduced from an introduction tube 303. At the same time, Group 5 element 3 different from nitrogen
07 is heated to produce a group 5 polyatomic molecule. The group V polyatomic molecule is decomposed by heating or the like in the dissociation chamber 308 to reduce the number of atoms in one molecule. For example, a Group 5 atom 309 consisting of one atom or a Group 5 diatomic molecule 310 consisting of two atoms is manufactured.

The Group 3 element 311 is heated and evaporated. Group 3 elements do not form polyatomic molecules and evaporate as group 3 atoms 312 which are monoatomic. A mixed crystal 302 is manufactured by simultaneously irradiating the substrate 301 with a group 5 atom 309 and a group 5 diatomic molecule 310 having a small number of atoms in one molecule and a nitrogen compound 305 and a group 3 atom 312. The substrate 301 has Ga
A semiconductor such as N or ZnO, sapphire, glass, or the like can be used. By controlling the material and temperature of the substrate 301, a mixed crystal 302 having a uniform crystal orientation or an amorphous mixed crystal 302 can be obtained.

Nitrogen and Group 5 elements other than nitrogen (P, As,
Sb, Bi) has a large difference in binding energy, and therefore, in general, mixed crystals containing both (GaNP, InGNA)
s, GaAlNAs, etc.). When the group V element 307 is heated, it evaporates in a group V polyatomic molecule composed of many atoms, mainly a molecular structure composed of four atoms called a tetramer. Group V polyatomic molecules have a small adhesion coefficient and low reactivity, so that the incorporation rate when producing the mixed crystal 302 is small, and it is difficult to control the composition ratio with nitrogen. Therefore, only a mixed crystal 302 containing a large amount of nitrogen and a small amount of a group V element other than nitrogen, or a mixed crystal 302 containing a large amount of a group V element other than nitrogen and a small amount of nitrogen can be produced.

Group 5 atoms 309 and Group 5 diatomic molecules 310 produced by decomposing group 5 polyatomic molecules have a higher adhesion coefficient and reactivity than tetramers and a higher incorporation rate into the mixed crystal 302. In addition, the composition ratio of nitrogen in the mixed crystal 302 and the other group V elements can be easily controlled. In particular, the group V atom 309 has high reactivity and can control the composition ratio of nitrogen and other group V elements over a wide range. That is, it is possible to produce a mixed crystal having a composition that cannot be produced by using a group 5 polyatomic molecule. In addition, the mixed crystal 302 manufactured using the group 5 atom 309 and the group 5 diatomic molecule 310 has a small composition fluctuation and a small electric resistance and thermal resistance. The emission spectrum is narrowed, and the optical characteristics are improved.

In this embodiment, two types of 5
Manufactured a 3-5 group semiconductor including a group, but is not limited to this.
A group 3-5 semiconductor including three or more types of group 5 may be manufactured. In addition, other mixed crystals such as chalcopyrite may be manufactured without being limited to the group 3-5 semiconductor.

In this embodiment, polyatomic molecules are decomposed by heat in the dissociation chamber. However, the present invention is not limited to this, and other methods such as electron irradiation and light irradiation may be used.

[Embodiment 3] A third embodiment of the present invention will be described with reference to FIG.
An embodiment will be described. A step of forming a group III-V semiconductor mixed crystal 302 containing nitrogen and a group V element other than nitrogen on the substrate 301 in a vacuum or atmosphere gas will be described. Introducing gaseous nitrogen compound 305 such as nitrogen molecules and ammonia
From 03, it is introduced into the dissociation chamber 304. In the dissociation chamber 304, excited nitrogen 306 is produced by plasma, optical excitation, or electronic excitation. Examples of the types of the excited nitrogen 306 include excited molecules of the nitrogen compound 305, molecules and atoms containing excited nitrogen called atomic nitrogen and radicals, and ionized molecules and atoms.

Simultaneously with the production of the excited nitrogen 306, a group V element 307 different from nitrogen is heated to produce a group V polyatomic molecule. The group 5 polyatomic molecule is decomposed by heating or the like in the dissociation chamber 308 to produce a group 5 atom 309 or a group 5 diatomic molecule 310. Further, the group 3 element 311 is heated and evaporated to produce a group 3 atom 312. Excited nitrogen 306 and group 5 atom 3
The mixed crystal 302 is manufactured by irradiating the substrate 301 with the 09 or group 5 diatomic molecule 310 and the group 3 atom 312.

The nitrogen compound 305 generally has low reactivity, and the temperature of the substrate 301 must be extremely high in order to produce the mixed crystal 302. Since the excited nitrogen 306 has high reactivity, the mixed crystal 302 can be manufactured without increasing the temperature of the substrate 301 too much. Group 5 atom 309 or Group 5 diatomic molecule 3 produced by decomposing Group 5 elements other than nitrogen
Since the mixed crystal 302 is manufactured using the 10 and the excited nitrogen 306, the composition of nitrogen and the group V element other than nitrogen in the mixed crystal 302 can be controlled in a wide substrate 301 temperature range. In addition, mixed crystal 3
02, the composition fluctuation is reduced, and the electrical resistance and the thermal resistance are reduced. Further, the emission spectrum becomes narrow.

In this embodiment, two types of 5
Manufactured a 3-5 group semiconductor including a group, but is not limited to this.
A group 3-5 semiconductor including three or more types of group 5 may be manufactured. In addition, other mixed crystals such as chalcopyrite may be manufactured without being limited to the group 3-5 semiconductor.

[Fourth Embodiment] FIG. 4 is a conceptual diagram for explaining a fourth embodiment of the present invention. A process of forming a Group 2-6 semiconductor mixed crystal 402 containing oxygen and a Group 6 element other than oxygen on the substrate 401 in a vacuum or an atmosphere gas will be described. A gaseous oxygen compound 405 such as an oxygen molecule is introduced from the introduction pipe 403. At the same time, group 6 element 4 different from oxygen
07 is heated to produce a group 6 polyatomic molecule. The group 6 polyatomic molecule is decomposed by heating or the like in the dissociation chamber 408 to obtain 1
Decrease the number of atoms in the molecule. For example, one atom consists of 6
A group 6 diatomic molecule 410 consisting of group atoms 409 and 2 atoms is produced.

The Group II element 411 is heated and evaporated. Group 2 elements do not form polyatomic molecules and evaporate as Group 2 atoms 412, which are monoatomic. A mixed crystal 402 is manufactured by simultaneously irradiating the substrate 401 with a group 6 atom 409 or a group 6 diatomic molecule 410 having a small number of atoms in one molecule and an oxygen compound 405 or a group 2 atom 412. The substrate 401 includes Ga
A semiconductor such as N, ZnO, or InP, sapphire, glass, or the like can be used. By controlling the material and temperature of the substrate 401, a mixed crystal 402 having a uniform crystal orientation and an amorphous mixed crystal 402 can be obtained.

Oxygen and a Group 6 element other than oxygen (S, Se,
Te) because the binding energy is significantly different from
In general, mixed crystals containing both (ZnOS, BeOSeTe, T
It is difficult to control the composition of eO). Generally, 6
The group 6 element easily forms polyatomic molecules, and when the group 6 element 407 is heated, it evaporates in a group 6 polyatomic molecular structure composed of many atoms. Assuming that the number of atoms in one molecule is n, sulfur (S) _forms a molecule called Sn and n becomes 8 at the maximum. Selenium (Se) also produces molecules consisting of up to eight atoms. Tellurium (Te) makes molecules consisting of one or two atoms.
Group 6 polyatomic molecules have a low adhesion coefficient and a low reactivity, so that the incorporation rate when producing the mixed crystal 402 is low, and it is difficult to control the composition ratio with oxygen.

Group 6 atoms 409 and group 6 diatomic molecules 410 produced by decomposing group 6 polyatomic molecules have a high adhesion coefficient and reactivity and a high incorporation rate into the mixed crystal 402, so that the mixed crystal 402 It becomes easy to control the composition ratio between oxygen and other Group 6 elements. In particular, group 6 atom 409 has high reactivity,
The composition ratio of oxygen to the other group 6 elements can be controlled over a wide range. That is, it is possible to produce a mixed crystal having a composition that cannot be produced using a group 6 polyatomic molecule. In addition, the mixed crystal 402 manufactured using the group 6 atom 409 and the group 6 diatomic molecule 410 has small composition fluctuation and low electric resistance and thermal resistance. The emission spectrum is narrowed, and the optical characteristics are improved.

In this embodiment, two types of 6
Group 2-6 semiconductors including group III, but not limited to this,
A group 2-6 semiconductor including three or more types of group 6 may be manufactured. In addition, other mixed crystals such as chalcopyrite may be manufactured without being limited to the group 2-6 semiconductor. Further, a mixed crystal such as TeO which is an optical recording material may be manufactured.

In this embodiment, the polyatomic molecules are decomposed by heat in the dissociation chamber. However, the present invention is not limited thereto, and the polyatomic molecules may be decomposed by other methods such as electron irradiation or light irradiation.

[Embodiment 5] Referring to FIG. 4, a fifth embodiment of the present invention will be described.
An embodiment will be described. A process of forming a Group 2-6 semiconductor mixed crystal 402 containing oxygen and a Group 6 element other than oxygen on the substrate 401 in a vacuum or an atmosphere gas will be described. A gaseous oxygen compound 405 such as oxygen molecule or H ₂ O is introduced into the inlet tube 403.
It is further introduced into the dissociation chamber 404. Excited oxygen 406 is produced in the dissociation chamber 404 by plasma, optical excitation, or electronic excitation. Examples of the types of the excited oxygen 406 include excited molecules of the oxygen compound 405, molecules and atoms containing excited oxygen called atomic oxygen and radicals, and ionized molecules and atoms.

At the same time as the production of the excited oxygen 406, a Group 6 element 407 different from oxygen is heated to produce a Group 6 polyatomic molecule. The group 6 polyatomic molecule is decomposed by heating or the like in the dissociation chamber 408 to produce a group 6 atom 409 or a group 6 diatomic molecule 410. Further, the group II element 411 is heated and evaporated to produce a group II atom 412. Excited oxygen 406 and group 6 atom 4
The mixed crystal 402 is manufactured by irradiating the substrate 401 with the 09 or group 6 diatomic molecule 410 and the group 2 atom 412.

The stable oxygen compound 405 generally has a low adhesion coefficient, and the substrate 401 must be irradiated with a large amount of the oxygen compound 405 to produce the mixed crystal 402. Since the excited oxygen 406 has a high adhesion coefficient, a small amount of the oxygen compound 4
05 can also produce a mixed crystal 402. Group 6 atoms 409 and Group 6 2 produced by decomposing Group 6 elements other than oxygen
Mixed crystal 402 using atomic molecules 410 and excited oxygen 406
To produce a mixed crystal 402 over a wide substrate 401 temperature range.
The composition of oxygen and the group 6 element other than oxygen can be controlled. Further, the composition fluctuation in the mixed crystal 402 is reduced, and the electrical resistance and the thermal resistance are reduced. Further, the emission spectrum becomes narrow.

In this embodiment, two types of 6
Group 2-6 semiconductors including group III, but not limited to this,
A group 2-6 semiconductor including three or more types of group 6 may be manufactured. In addition, other mixed crystals such as chalcopyrite may be manufactured without being limited to the group 2-6 semiconductor. Further, a mixed crystal such as TeO which is an optical recording material may be manufactured.

[Embodiment 6] FIG. 5 is a schematic view of a manufacturing apparatus for explaining a sixth embodiment of the present invention, and FIG.
FIG. 6B is a conceptual diagram for explaining a manufacturing method, and FIG.
Is a conceptual diagram for explaining a conventional technique.

The step of forming a Group 2-6 semiconductor mixed crystal 502 containing sulfur (S) and selenium (Se) on a substrate 501 in a vacuum or atmosphere gas will be described. The sulfur 503 is heated to produce the S polyatomic molecule 606. S polyatomic molecule 60
As 6, such as _{S 4, S 5, S 6} , S 7, S 8 are formed. Decomposed by heating the S polyatomic molecules 606 a dissociation chamber 504, atomic number n in one molecule to produce a smaller S _n 601. In _Sn 601, the proportion of molecules having small n such as atomic S and S ₂ composed of two atoms is large.

At the same time, selenium 505 is heated to produce Se polyatomic molecules 607. As the Se polyatomic molecule 607, Se ₄ , Se ₅ , Se ₆ , Se ₇ , Se _{8 and the} like are formed. The Se polyatomic molecules 607 decompose by heating in dissociation chamber 506, 1 atom number n in the molecule is small Se _n 6
02 is manufactured. The proportion of small molecules Se _n consists atomic Se or 2 atoms in 602 like Se ₂ n is large.

The Group II element 507 is heated and evaporated. Group 2 elements do not form polyatomic molecules and evaporate as Group 2 atoms 603, which are monoatomic. 1 number of atoms in the molecule is less S _n 601, by irradiating the Se _n 602 at the same time as the substrate 501 and a group 2 atoms 603 to produce a mixed crystal 502. Substrate 5
For 01, a semiconductor such as GaAs, InP, Si, or CdS, sapphire, glass, or the like can be used. By controlling the material and temperature of the substrate 501, a mixed crystal 502 having a uniform crystal orientation and an amorphous mixed crystal 502 can be obtained.

FIG. 6A shows the surface of the mixed crystal 502 thus manufactured. Due to the use of 1 atomic group 6 fewer molecules S _n 601 in the molecule and the Se _n 602, mixed 5
On the surface 02, S604 and Se605 are uniformly mixed, and a mixed crystal 502 having less composition fluctuation is obtained. On the other hand, when the mixed crystal 502 is manufactured using the S polyatomic molecule 606, the Se polyatomic molecule 607, and the Group 2 atom 603,
As shown in FIG. 6B, since a region where S604 is gathered and a region where group 6 atoms 605 are gathered are formed on the surface of the mixed crystal 502, a mixed crystal having a very large composition fluctuation is formed.
This is because there is a high probability that the S polyatomic molecules 606 and Se polyatomic molecules 607 containing a large number of atoms of at most 8 adhere to the surface of the mixed crystal 502 and are taken into the mixed crystal 502 as they are.

As shown in FIG. 6A, in the mixed crystal 502 having a small composition fluctuation, the electric resistance and the thermal resistance are small.
It shows excellent characteristics when used in semiconductor devices. Further, the forbidden band width becomes constant, and an optical device having a narrow emission spectrum can be obtained. Such an improvement in characteristics is due to _Sn 601
And Se atoms n included in the _n 602 is not only when one or two, the average value of S polyatomic molecules 606 and Se
Appears when the number is smaller than the number of atoms in a polyatomic molecule.

In the mixed crystal 502 having a large composition fluctuation as shown in FIG. 6B, the potential for carriers is not periodic, so that a phenomenon called Anderson localization is likely to occur, and the electrical resistance increases and the thermal resistance increases. increase,
Characteristics that are inconvenient for ordinary electric elements, such as broadening of the emission spectrum, become stronger. In particular, the resistance of the p-type layer becomes extremely high because the potential at the valence band edge fluctuates greatly.
Such a composition fluctuation can be remarkably suppressed when both the S polyatomic molecule 606 and the Se polyatomic molecule 607 are decomposed as compared with the case where both are decomposed. further,
If a disassembled both sticking coefficient of both S _n 601 and Se _n 602 is increased, it is possible to manufacture in a wide substrate 501 temperature range.

In this embodiment, one type of 2
A Group 2-6 semiconductor including a Group 6 element and two types of Group 6 was manufactured, but not limited thereto.
A group 2-6 semiconductor containing two or more group 2 elements such as e, Zn, Cd, Hg, Mg, Ca, Sr, and Ba may be manufactured. In addition, other mixed crystals such as chalcopyrite may be manufactured without being limited to the group 2-6 semiconductor.

In this embodiment, polyatomic molecules are decomposed by heat in the dissociation chamber. However, the present invention is not limited to this, and other methods such as electron irradiation and light irradiation may be used. Alternatively, a compound having a small number of atoms may be manufactured by heating and evaporating a compound having a high decomposition temperature such as ZnS or CdSe.

[Embodiment 7] FIG. 7A shows a seventh embodiment of the present invention.
FIG. 7 is a conceptual diagram for explaining the embodiment of FIG.
(B) is a conceptual diagram for explaining a conventional technique.

The substrate is placed on a substrate 701 in a vacuum or an atmosphere gas.
Group 2-6 semiconductor mixed containing Au (S) and Tellurium (Te)
The step of forming the crystal 702 will be described. Heat sulfur and S
Produce polyatomic molecule 708. S polyatomic molecule 708
And S_Two, S_Three, S_Four, S_Five, S ₆, S₇, S₈Etc are formed
It is. Decompose the S polyatomic molecule 708 by heating or the like,
S with small number of atoms n in one molecule_n703 is manufactured. same
Sometimes tellurium is heated to produce Te molecules 709. Te
Lulu is Te whose atom number n is 2._n704. Ma
Further, the group 2 element is heated and evaporated to form a monoatomic state 2
A group atom 705 is produced.

S _n 703 having a small number of atoms in one molecule and T
by irradiating and e _n 704 and group 2 atoms 705 simultaneously with the substrate 701 to produce a mixed crystal 702. The substrate 701 has GaAs
Semiconductors such as s, InP, Si, and ZnSe, glass, and the like can be used. Mixed crystal 7 thus produced
02 is as shown in FIG. 7A, and S706 and Te
707 are mixed uniformly, and a mixed crystal 702 having a small composition fluctuation
Is obtained.

On the other hand, the S polyatomic molecule 708 and Te
When the mixed crystal 702 is manufactured using the molecule 709 and the group 2 atom 705, as shown in FIG.
Since a region where S706 is gathered and a region where Te707 are gathered are formed on the surface, a mixed crystal having an extremely large composition fluctuation is formed. This is because there is a high probability that S polyatomic molecules 708 containing a large number of atoms of a maximum of 8 will adhere to the surface of the mixed crystal 702 and be taken into the mixed crystal 702 as it is, and that Te707 will adhere to the surface. This is because S706 is easily replaced by S706 due to the difference in chemical bonding property, and Te707 remains only in the region where S706 is not attached.

As shown in FIG. 7A, in the mixed crystal 702 having a small composition fluctuation, the electric resistance and the thermal resistance are small.
It shows excellent characteristics when used in semiconductor devices. Further, the forbidden band width becomes constant, and an optical element having a narrow emission spectrum can be obtained. Further, the mixture becomes miscible under a wide range of growth conditions, and a mixed crystal having an arbitrary composition can be obtained. Improvement of such properties, not only when the number of atoms n included in S _n 703 is 1 or 2, the average value is obtained when less than the number of atoms in S polyatomic molecules 708.

In the mixed crystal 702 having a large composition fluctuation as shown in FIG. 7B, the potential for carriers is not periodic, so that a phenomenon called Anderson localization is likely to occur, and the electrical resistance increases and the thermal resistance decreases. increase,
Characteristics that are inconvenient for ordinary electric elements, such as broadening of the emission spectrum, become stronger. In particular, since the electronegativities of S706 and Te707 are very different, the fluctuation of the potential at the valence band edge is large, and the resistance of the p-type layer becomes very high. In addition, since the atomic radii of S706 and Te707 are large, when S polyatomic molecule 708 is used, immiscibility appears, three-dimensional growth easily occurs, and it is difficult to obtain a crystal with few defects.

In this embodiment, one type of 2
A Group 2-6 semiconductor including a Group 6 element and two types of Group 6 was manufactured, but not limited thereto.
A group 2-6 semiconductor containing two or more group 2 elements such as e, Zn, Cd, Hg, Mg, Ca, Sr, and Ba may be manufactured. In addition, other mixed crystals such as chalcopyrite may be manufactured without being limited to the group 2-6 semiconductor.

In this embodiment, the S polyatomic molecule is decomposed by heat. However, the present invention is not limited to this, and the S polyatomic molecule may be decomposed by another method such as electron irradiation or light irradiation. Further, S molecules having a small number of atoms may be produced by heating and evaporating a compound such as ZnS or CdS.

[Embodiment 8] FIG. 8A shows an eighth embodiment of the present invention.
FIG. 8 is a conceptual diagram for explaining the embodiment of FIG.
FIG. 9B is a conceptual diagram for explaining a conventional technique, and FIG. 9 is a band diagram.

A step of forming a Group 2-6 semiconductor mixed crystal 802 containing selenium (Se) and tellurium (Te) on a substrate 801 in a vacuum or an atmosphere gas will be described. Selenium is heated to produce Se polyatomic molecules 808. Se polyatomic molecule 80
8, Se ₂ , Se ₃ , Se ₄ , Se ₅ , Se ₆ , S
e ₇ , Se _{8 and the} like are formed. Decomposed by heating the Se polyatomic molecules 808, atomic number n in one molecule to produce a small Se _n 803. At the same time, tellurium is heated to T
e molecule 809 is produced. Tellurium is a Te _n 804 the number n of atoms is 2. Further, the group 2 element is heated and evaporated to produce a group 2 atom 805 which is in a monoatomic state.

[0070] to produce a mixed crystal 802 by irradiating atoms in one molecule is less Se _n 803 and Te _n 804 and a group 2 atoms 805 at the same time the substrate 801. The substrate 801 includes Ga
Semiconductors such as As, InP, Si, ZnSe, and CdS, glass, and the like can be used. The surface of the mixed crystal 802 thus manufactured is as shown in FIG.
806 and Te807 are uniformly mixed, and a mixed crystal 802 with small composition fluctuation is obtained.

On the other hand, the Se polyatomic molecule 808 and T
When the mixed crystal 802 is manufactured using the e molecule 809 and the group 2 atom 805, as shown in FIG.
Since a region where Se 806 and a region where Te 807 are gathered are formed on the two surfaces, a mixed crystal having a very large composition fluctuation is formed. This is because there is a high probability that Se polyatomic molecules 808 containing a large number of atoms of up to eight adhere to the surface of the mixed crystal 802 and are taken into the mixed crystal 802 as it is, and that Te807 adheres to the surface. Is also easily replaced with Se806 due to the difference in chemical bonding,
This is because Te807 remains only in the area where No. 6 did not adhere.

FIG. 9 shows the difference in band structure depending on the presence or absence of composition fluctuation. In the mixed crystal 802 having a small composition fluctuation shown in FIG. 8A, the valence band edge 901 and the conduction band edge 902
Is constant regardless of the position in the mixed crystal 802 as shown in FIG. For this reason, scattering to carriers is small,
Electric resistance is small. In addition, since scattering against lattice vibration is small, the semiconductor device has excellent heat resistance and small characteristics. Further, the forbidden band width is constant irrespective of the position, and an optical element having a narrow emission and absorption spectrum can be obtained. In addition, the shift between the light emitting end and the absorption end is reduced. Improvement of such properties, not only when the number of atoms n included in Se _n 803 is 1 or 2, the average value is obtained when less than the number of atoms in the Se polyatomic molecules 808.

In the mixed crystal 802 having a large compositional fluctuation shown in FIG. 8B, the potential for carriers is not periodic, so that the valence band edge 901 and the conduction band edge 90
2 changes depending on the position as shown in FIG. In particular,
Since the electronegativities of Se806 and Te807 are very different, the potential of the valence band edge 901 greatly fluctuates. For this reason, a phenomenon called Anderson localization occurs, and holes are trapped in low energy portions, resulting in a very high resistance of the p-type layer. In addition, scattering against lattice vibration is large, and thermal resistance increases. Since the valence band edge 901 and the conduction band edge 902 differ depending on the position, the forbidden band width fluctuates in the mixed crystal 802, so that the emission spectrum and the absorption spectrum are widened or the emission edge and the absorption edge are shifted. Such characteristics are inconvenient for ordinary electric elements and optical elements.

In this embodiment, one type of 2
A Group 2-6 semiconductor including a Group 6 element and two types of Group 6 was manufactured, but not limited thereto.
A group 2-6 semiconductor containing two or more group 2 elements such as e, Zn, Cd, Hg, Mg, Ca, Sr, and Ba may be manufactured. In addition, other mixed crystals such as chalcopyrite may be manufactured without being limited to the group 2-6 semiconductor.

In this embodiment, the Se polyatomic molecule is decomposed by heat. However, the present invention is not limited to this, and the Se polyatomic molecule may be decomposed by another method such as electron irradiation or light irradiation. Further, a Se molecule having a small number of atoms may be manufactured by heating and evaporating a compound such as ZnSe or CdSe.

Ninth Embodiment A ninth embodiment of the present invention will be described with reference to FIGS. In the seventh embodiment, Te molecules 709 are manufactured by heating tellurium, and the Te molecules 709 are decomposed by heating or the like to manufacture Te _n 704 in which the number n of atoms is 1. Atoms in one molecule is small and S _n 703 and Te _n 704 and a group 2 atoms 705 simultaneously irradiating the substrate 701 to produce a mixed crystal 702.

Even if Te707 adheres to the surface, it has the property of being easily replaced by S706 due to the difference in chemical bonding properties. Therefore, it is necessary to supply an excessive amount of Te707 in order to control the mixed crystal composition. Compared to Te molecule 709, atomic T
e _n 704 is highly reactive, sticking coefficient is high. Therefore, by decomposing the Te molecules 709, a wide substrate 7
The production of the mixed crystal 702 in the temperature range of 01 is possible, the conditions for the incorporation are widened, and the composition fluctuation is further reduced. In addition, material consumption can be reduced.

In the eighth embodiment, tellurium is heated to T
An e molecule 809 is manufactured, and the Te molecule 809 is decomposed by heating or the like, thereby manufacturing a Te _n 804 in which the number n of atoms is 1. Se _n 803 atoms in one molecule is small and Te _n 8
The mixed crystal 802 is manufactured by simultaneously irradiating the substrate 801 with the group 04 and the group 805 atoms.

Even if Te807 adheres to the surface, it is easily replaced with Se806 due to a difference in chemical bonding property. Therefore, it is necessary to supply an excessive amount of Te807 to control the mixed crystal composition. Compared with Te molecule 809, atomic Te _n 804 is highly reactive, sticking coefficient is high. For this reason, by decomposing the Te molecules 809, it becomes possible to manufacture the mixed crystal 802 in a wide temperature range of the substrate 801 and the conditions for the incorporation are widened and the composition fluctuation is further reduced. In addition, material consumption can be reduced.

In this embodiment, one type of 2
A Group 2-6 semiconductor including a Group 6 element and two types of Group 6 was manufactured, but not limited thereto.
A group 2-6 semiconductor containing two or more group 2 elements such as e, Zn, Cd, Hg, Mg, Ca, Sr, and Ba may be manufactured. In addition, other mixed crystals such as chalcopyrite may be manufactured without being limited to the group 2-6 semiconductor.

In this embodiment, the Te molecule is decomposed by heat. However, the present invention is not limited to this. The Te molecule may be decomposed by another method such as electron irradiation or light irradiation. Further, atomic Te may be produced by heating and evaporating a compound such as ZnTe or CdTe.

[Embodiment 10] FIG. 10A is a conceptual diagram for explaining a tenth embodiment of the present invention, and FIG. 10B is a conceptual diagram for explaining a conventional technique. is there.

A step of adding nitrogen as an impurity to the group 2-6 semiconductor mixed crystal 1002 containing selenium (Se) and tellurium (Te) on the substrate 1001 in a vacuum or atmosphere gas will be described. Selenium is heated to produce Se polyatomic molecule 1010. Decomposed by heating the Se polyatomic molecules 1010, atomic number n in one molecule to produce a small Se _n 1003. At the same time, the tellurium is heated to produce Te molecules 1011. Te _n 1004 tellurium number n of atoms is 2
Becomes In addition, a group 2 element is heated and evaporated to form a group 2 atom 1
005 is manufactured. A nitrogen plasma 1006 is manufactured by applying a high frequency or the like to the nitrogen gas.

[0084] Se _n 1003, Te _n 1004,2 group atoms 1005, nitrogen plasma 1006 simultaneously substrate 1001
To produce a mixed crystal 1002. The surface of the mixed crystal 1002 thus manufactured is as shown in FIG. 10A. Se1007 and Te1008 are uniformly mixed, the composition fluctuation is small, and N1009 has a uniform density.
2

On the other hand, Se polyatomic molecule 1010, Te molecule 1011, group 2 atom 1005, nitrogen plasma 1
In the case where the mixed crystal 1002 is manufactured by using No. 006, as shown in FIG.
Since a region where 07 and a region where Te 1008 are gathered is formed, a mixed crystal 1002 having a very large composition fluctuation is obtained. N1009 is mainly taken into a region where the Se polyatomic molecule 1010 does not fly, that is, a region where Te1008 is gathered. Therefore, the concentration of N1009 is not uniform in mixed crystal 1002, and the density locally increases. This is because selenium, which has a much stronger bonding force with group 2 elements than nitrogen, has a Se polyatomic molecule 1010 structure and a mixed crystal 10
02 in the area where Te1008 is gathered, because N1009 flies to the surface and cannot be bonded in that area.
This is due to the high uptake rate.

As shown in FIG. 10A, when N1009 is uniformly distributed, N1009 becomes an acceptor,
Mixed crystal 1002 shows p-type conduction characteristics. Further, generation of crystal defects is small. On the other hand, as shown in FIG.
If 1009 is locally high in density, two N100s
The probability of adjacent 9's becomes high, and they will not work as acceptors, and the resistance of mixed crystal 1002 will be high. Crystal defects are also likely to occur.

In this embodiment, one type of 2
Although a Group 2-6 semiconductor containing a Group 6 element, selenium, and tellurium was manufactured, the present invention is not limited to this, and mixed crystals containing two or more other 6 Groups, Be, Zn, Cd, Hg, Mg, Ca, Sr , Ba
For example, a Group 2-6 semiconductor containing two or more Group 2 elements may be manufactured. In addition, other mixed crystals such as chalcopyrite may be manufactured without being limited to the group 2-6 semiconductor.

[Embodiment 11] FIG. 11 shows an eleventh embodiment of the present invention.
FIG. 5 is a diagram illustrating a relationship between a forbidden band width and a lattice constant for describing the embodiment.

In the sixth embodiment, the substrate 501 is made of GaP
And the number of atoms in one molecule is small S _n601, Se_n60
2 and Be and Mg as group 2 atoms 603
Irradiating the substrate 501 with BeMg lattice-matched to the substrate 501
The SSe mixed crystal 502 can be manufactured. As shown in FIG.
As shown, the forbidden band width is 4 eV or more
Crystal 502 is obtained. S with a small number of atoms in one molecule_n6
01, Se_n602, the doping characteristics
And the electrical resistance can be reduced.

In this embodiment, GaP is used for the substrate. However, as can be seen from FIG. 11, the BeMgSSe mixed crystal 502 can be lattice-matched even if ZnS having a lattice constant close to that of GaP is used.

[0091] Further, in the embodiment 6, the substrate 501 and GaAs, atomic number less S _n 601 in one molecule,
And Se _n 602, may be irradiated at the same time the substrate 501 Mg and Zn as a Group 2 atoms 603, to produce a MgZnSSe mixed crystal 502 lattice matched to the substrate 501.
As shown in FIG. 11, a wide-gap mixed crystal 502 having a forbidden band width of 2.6 to 4 eV is obtained. Since the number of atoms in one molecule is used less S _n 601, Se _n 602,
When nitrogen is added by nitrogen plasma, a p-type layer having a high concentration can be obtained. Further, composition fluctuation is reduced, and electric resistance and thermal resistance are reduced.

In this embodiment, GaAs is used for the substrate. However, as can be seen from FIG. 11, even if ZnSe having a lattice constant close to that of GaAs is used, the MgZnSSe mixed crystal 502 can be lattice-matched.

[Twelfth Embodiment] A twelfth embodiment of the present invention will be described with reference to FIG. In embodiments 7, S _n 703 atoms in one molecule is small and Te _n 704
By irradiating the GaP substrate 701 simultaneously with Be and Zn as group II and group 705 atoms, a BeZnSTe mixed crystal 702 can be manufactured. As shown in FIG. 11, the forbidden band width is 3e.
A mixed crystal 502 having a wide gap of V or more is obtained. Since it contains tellurium, p-type doping can be easily obtained.

In this embodiment, GaP is used for the substrate, but ZnS may be used as shown in FIG.
The mixed crystal was MgZnSTe, the substrate was GaAs,
nP, InAs, GaSb, ZnSe, CdS, CdS
It may be any of e. In addition, the mixed crystal is MgCdST
e, and the substrate is InP, InAs, GaSb, CdS,
Any of CdSe and ZnTe may be used.

[Thirteenth Embodiment] A thirteenth embodiment of the present invention will be described with reference to FIG. In embodiments 8, Se _n 803 atoms in one molecule is small and Te _n 80
By irradiating the InP substrate 801 simultaneously with Mg and Zn as Group 4 and Group 2 atoms 805, a MgZnSeTe mixed crystal 802 can be manufactured. As shown in FIG. 11, the forbidden band width is 2
, A wide-gap mixed crystal 502 of 4 eV is obtained.
Since the number of atoms in one molecule is used less Se _n 803 and Te _n 804, the addition of nitrogen in the nitrogen plasma high density with a small resistance p-type layer. Also, an n-type layer is obtained. Further, the composition fluctuation of MgSe and ZnTe generated due to the fact that Mg is easily bonded to Se806 is reduced, and the electric resistance and the thermal resistance are reduced.

In this embodiment, InP is used for the substrate. However, as can be seen from FIG. 11, InAs, GaSb, C
Any of dS, CdSe, and ZnTe may be used.
The mixed crystal is BeZnSeTe, the substrate is GaAs,
Any of ZnSe may be used. In addition, mixed crystal
dSeTe and the substrate is InAs, GaSb, CdS
e or ZnTe.

[Embodiment 14] FIG. 12A is a conceptual diagram for explaining a fourteenth embodiment of the present invention, and FIG. 12B is a conceptual diagram for explaining a conventional technique. is there.

A step of adding nitrogen as an impurity to the group 2-6 semiconductor mixed crystal 1202 containing selenium on the substrate 1201 in a vacuum or an atmosphere gas will be described. Selenium is heated to produce Se polyatomic molecule 1208. Decomposed by heating the Se polyatomic molecules 1208, atomic number n in one molecule to produce a small Se _n 1203. At the same time, the group 2 element is heated and evaporated to produce a group 2 atom 1204.
Nitrogen plasma 1205 by applying high frequency or the like to nitrogen gas
To manufacture.

[0099] Se _n 1203,2 group atoms 1204, by irradiating the substrate simultaneously 1201 nitrogen plasma 1205 to produce a mixed crystal 1202. Mixed crystal 12 thus produced
02 is as shown in FIG.
Adhered uniformly, and N1207 was also mixed crystal 1202 with uniform density.
It is taken in.

On the other hand, when the mixed crystal 1202 is manufactured using the Se polyatomic molecule 1208, the group II atom 1204, and the nitrogen plasma 1205, as shown in FIG. N1207 is mainly taken into the region where the Se polyatomic molecule 1208 did not fly. Therefore, the concentration of N1207 is not uniform in mixed crystal 1202, and the density locally increases. This is because selenium, which has a much stronger bonding force with Group 2 elements than nitrogen, flies to the surface of the mixed crystal 1202 with a Se polyatomic molecule 1208 structure, and N1207 cannot be bonded in that region.

As shown in FIG. 12A, when N1207 is uniformly distributed, N1207 becomes an acceptor,
The mixed crystal 1202 exhibits p-type conduction characteristics, and the doping concentration can be increased several times. Further, generation of crystal defects is small. On the other hand, as shown in FIG.
When the concentration is locally high, the probability that two N 1207 are adjacent to each other increases, and the N 1207 does not work as an acceptor, and the resistance of the mixed crystal 1202 increases. Crystal defects are also likely to occur.

In this embodiment, one type of 2
Although a Group 2-6 semiconductor containing a Group 2 element is manufactured, the present invention is not limited to this, and a Group 2-6 semiconductor containing 2 or more Group 2 elements may be manufactured. In addition, other mixed crystals such as chalcopyrite may be manufactured without being limited to the group 2-6 semiconductor.

In the above embodiment, the mixed crystal was BeMg
ZnSe may be used, and the substrate may be made of either GaAs or ZnSe. Further, the mixed crystal may be made of MgZnCdSe, and the substrate may be made of either InP or CdS.

[Embodiment 15] Referring to FIG. 1 and FIG.
A fifteenth embodiment of the present invention will be described. The group V polyatomic molecule 29 is introduced into the dissociation chamber 16 and irradiated with an electron beam. The group 5 polyatomic molecule 29 is decomposed by collision with an electron to form a group 5 atom 2
A group 3 or group 5 diatomic molecule 24 is produced. Ionized group 5 atoms 23 and group 5 diatomic molecules 24 are also produced.

In this embodiment, the group V polyatomic molecule is irradiated with an electron beam. However, the present invention is not limited to this, and high-energy light may be irradiated. Further, irradiation with ions such as argon may be performed. Alternatively, a high frequency or microwave may be applied to turn the group 5 polyatomic molecule into plasma to decompose or excite it.

In the above embodiment, a group 5 polyatomic molecule is used. However, the present invention is not limited to this, and a group 6 polyatomic molecule may be used.

[Embodiment 16] In Embodiment 1, the manufacturing apparatus can be a molecular beam crystal growth apparatus for forming a film in a vacuum. Group 5 atom 23 or Group 5 diatomic molecule 2
When 4 collide with each other, a group 5 polyatomic molecule 29 is formed. In a vacuum, the group 5 atoms 23 and the group 5 diatomic molecules 24 reach the substrate 11 without collision, and the mixed crystal 12 can be manufactured.

In this embodiment, a molecular beam crystal growth apparatus is used, but another vacuum apparatus such as a vacuum sputtering apparatus may be used.

In the above embodiment, a group 5 polyatomic molecule is used. However, the present invention is not limited to this, and a group 6 polyatomic molecule may be used.

[0110] [Embodiment 17] In embodiment 7, by heating the substrate 701 to 200 ° C. from 100, S _n 703 atoms in one molecule is small and Te _n 704 and group 2 atoms 70
5 is simultaneously applied to the substrate 701 to produce a mixed crystal 702. Since sulfur and tellurium have significantly different atomic radii and adhesion coefficients, when S polyatomic molecule 708 is used, S706 and Te707 are not mixed at such a substrate temperature, and are in an immiscible state. If the distribution of S706 and Te707 on the surface of the mixed crystal 702 is not uniform, immiscibility tends to occur. S706 and distribution of Te707 in mixed crystal 702 surface by using a S _n 703 and Te _n 704 becomes uniform, not the immiscible less mixed crystal 702 in composition fluctuations can be obtained.

In this embodiment, sulfur and tellurium are used as Group 6 elements, but other Group 6 elements and Group 5 elements may be used.

[Embodiment 18] FIG. 13 shows an eighteenth embodiment of the present invention.
It is a key map of a light emitting element showing an embodiment. Substrate 130
After forming an n-cladding layer 1302 and an active layer 1303 on the substrate 1 by a conventional manufacturing method, the mixed crystal 1 shown in Embodiment 10 is formed.
002 is manufactured as a p-cladding layer 1304. Subsequently, the metal is evaporated to form a p-electrode 1305 and an n-electrode 1306. A voltage is applied to the p-electrode 1305 and the n-electrode 1306 to cause the active layer 1303 to emit light. When manufactured by a conventional method, the p-cladding layer 1304 becomes a mixed crystal having a large composition fluctuation as shown in FIG. On the other hand, as shown in FIG. 10A, the p-cladding layer 1304 manufactured according to the present invention has no composition fluctuation and is structurally different. Since there is no composition fluctuation, p
A light-emitting element having a low operating voltage with a low resistance of the cladding layer 1304 can be obtained. Further, the thermal resistance is small and a high light output is obtained.

In this embodiment, a light emitting element is used.
The present invention is not limited to this, and may be used for other optical elements such as a light receiving element and a modulation element.

[Embodiment 19] FIG. 14 shows a nineteenth embodiment of the present invention.
It is a key map of an electronic semiconductor element showing an embodiment. After an n-layer 1402 is manufactured on a substrate 1401 by a conventional manufacturing method, impurities are added to the mixed crystal 12 shown in the first embodiment to manufacture a p-layer 1403 and an n-layer 1404. Subsequently, a metal is deposited to form an emitter 1405, a base 1406, and a collector 1407. A voltage is applied between the emitter 1405, the base 1406, and the collector 1407 to amplify the signal. Fabricated by conventional methods, the p-layer 140
3. The n-layer 1404 becomes a mixed crystal having a large composition fluctuation as shown in FIG. On the other hand, the p-layer 1403 and the n-layer 1404 manufactured according to the present invention have no structural fluctuation and are structurally different as shown in FIG. Since there is no composition fluctuation, the p-layer 1403,
A transistor with low resistance of the n-layer 1404 and excellent high-frequency characteristics can be obtained.

In this embodiment, a transistor is used as the electronic semiconductor element. However, the present invention is not limited to this, and another electronic element such as a diode may be used.

[0116]

According to the method for producing a multicomponent mixed crystal according to the present invention, a multicomponent mixed crystal having a small composition modulation can be produced with good reproducibility.

[Brief description of the drawings]

FIG. 1 is a schematic diagram of a manufacturing apparatus for explaining a first embodiment of the present invention.

2A is a conceptual diagram for explaining a manufacturing method, and FIG. 2B is a conceptual diagram for explaining a conventional technique.

FIG. 3 is a conceptual diagram for explaining a second embodiment of the present invention.

FIG. 4 is a conceptual diagram for explaining a fourth embodiment of the present invention.

FIG. 5 is a schematic view of a manufacturing apparatus for explaining a sixth embodiment of the present invention.

6A is a conceptual diagram for explaining a manufacturing method, and FIG. 6B is a conceptual diagram for explaining a conventional technique.

FIG. 7A is a conceptual diagram for explaining a seventh embodiment of the present invention, and FIG. 7B is a conceptual diagram for explaining a conventional technique.

FIG. 8A is a conceptual diagram for explaining an eighth embodiment of the present invention, and FIG. 8B is a conceptual diagram for explaining a conventional technique.

FIG. 9 is a band diagram.

FIG. 10A is a conceptual diagram for explaining a tenth embodiment of the present invention, and FIG. 10B is a conceptual diagram for explaining a conventional technique.

FIG. 11 is a diagram illustrating a relationship between a forbidden band width and a lattice constant for explaining an eleventh embodiment of the present invention.

FIG. 12A is a conceptual diagram illustrating a fourteenth embodiment of the present invention, and FIG. 12B is a conceptual diagram illustrating a conventional technique.

FIG. 13 is a conceptual diagram of a light emitting device showing an eighteenth embodiment of the present invention.

FIG. 14 is a conceptual diagram of an electronic semiconductor device showing a nineteenth embodiment of the present invention.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 11 Substrate 12 Mixed crystal 13 Antimony (Sb) 14 Dissociation chamber 15 Group 5 element 16 Dissociation chamber 17 Group 3 element 21 Sb 22 Sb ₂ 23 Group 5 atom 24 Group 2 atom molecule 25 Group 3 atom 26 Sb 27 Group 5 atom 28 Sb polyatomic molecule 29 Group 5 polyatomic molecule 301 Substrate 302 Mixed crystal 303 Introducing tube 304 Dissociation chamber 305 Nitrogen compound 306 Excited nitrogen 307 Group 5 element 308 Dissociation chamber 309 Group 5 atom 310 Group 5 diatomic molecule 311 Group 3 element 312 3 Group atom 401 substrate 402 mixed crystal 403 introduction tube 404 dissociation chamber 405 oxygen compound 406 excited oxygen 407 group 6 element 408 dissociation chamber 409 group 6 atom 410 group 6 diatomic molecule 411 group 2 element 412 group 2 atom 501 substrate 502 mixed crystal 503 Sulfur 504 Dissociation chamber 505 Selenium 506 Dissociation chamber 507 Group 2 element 01 S _n 602 Se _n 603 2 group atoms 604 S 605 Se 606 S polyatomic molecules 607 Se polyatomic molecules 701 substrate 702 mixed crystal 703 S _n 704 Te _n 705 2 group atoms 706 S 707 Te 708 S polyatomic molecules 709 Te molecules 801 substrate 802 mixed crystal 803 Se _n 804 Te _n 805 2 group atoms 806 Se 807 Te 808 Se polyatomic molecules 809 Te molecules 901 valence band edge 902 conduction band edge 1001 substrate 1002 mixed crystal 1003 Se _n 1011 Te molecules 1004 Te _n 1005 2 group atoms 1006 nitrogen plasma 1007 Se 1008 Te 1009 n 1010 Se polyatomic molecules 1201 substrate 1202 mixed crystal 1203 Se _n 1204 2 group atoms 1205 nitrogen plasma 1206 Se 1207 n 1208 Se Tahara Molecular 1301 substrate 1302 n-cladding layer 1303 active layer 1304 p-cladding layer 1305 p electrode 1306 n electrode 1401 substrate 1402 n layer 1403 p layer 1404 n layer 1405 emitter 1406 base 1407 Collector

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁷ , DB name) H01L 21/203 H01L 21/205 H01L 21/31 H01L 21/365 C23C 14/00 C23C 16/00 C30B 25 / 00 C30B 29/00

Claims (20)

(57) [Claims] In a mixed crystal film containing antimony and a group V element other than antimony, a step of evaporating polyatomic molecules of antimony, and a step of decomposing the polyatomic molecules of antimony to reduce the molecular number of the atoms. A step of evaporating a polyatomic molecule of a group V element other than the antimony; a step of decomposing a polyatomic molecule of a group V element other than the antimony to produce a molecule having a small number of atoms; Producing a mixed crystal using a molecule having a small number of atoms of antimony and a molecule having a small number of atoms of a group V element other than the antimony as a raw material. 2. A mixed crystal film containing nitrogen and a group V element other than nitrogen, wherein a step of evaporating a polyatomic molecule of the group V element other than nitrogen is performed, and A method for producing a multi-element mixed crystal, comprising: a step of decomposing an atomic molecule to produce a molecule having a small number of atoms; and a step of producing the mixed crystal using the molecule having a small number of atoms as a raw material. 3. A method comprising: exciting a nitrogen molecule or a nitrogen compound to form an excited molecule or an excited atom; and manufacturing the mixed crystal using the excited molecule or the excited atom as a raw material. Item 4. The method for producing a multicomponent mixed crystal according to Item 2. 4. A mixed crystal film containing oxygen and a group 6 element other than oxygen, wherein a step of evaporating a polyatomic molecule of the group 6 element other than oxygen is performed, and A method for producing a multi-element mixed crystal, comprising: a step of decomposing an atomic molecule to produce a molecule having a small number of atoms; and a step of producing the mixed crystal using the molecule having a small number of atoms as a raw material. 5. A method comprising: exciting oxygen molecules or oxygen compounds to form excited molecules or excited atoms; and producing the mixed crystal using the excited molecules or excited atoms as a raw material. Item 5. A method for producing a multicomponent mixed crystal according to Item 4. 6. In a mixed crystal film containing sulfur and selenium, a step of evaporating polyatomic molecules of sulfur, and a step of decomposing the polyatomic molecules of sulfur to produce a molecule having a small number of atoms. Evaporating polyatomic molecules of selenium;
A step of decomposing the polyatomic molecule of selenium to produce a molecule having a small number of atoms, and a step of producing the mixed crystal using the molecules having a small number of atoms of the sulfur and the molecules having a small number of atoms of the selenium as raw materials. A method for producing a multicomponent mixed crystal, comprising: 7. In a mixed crystal film containing sulfur and tellurium, a step of evaporating polyatomic molecules of sulfur, and a step of decomposing the polyatomic molecules of sulfur to produce a molecule having a small number of atoms. Producing the mixed crystal using a molecule having a small number of sulfur atoms as a raw material. 8. A method for producing a mixed crystal film containing selenium and tellurium, comprising: evaporating polyatomic molecules of selenium; and decomposing the polyatomic molecules of selenium to produce molecules having a small number of atoms. Producing the mixed crystal using a molecule having a small number of atoms of selenium as a raw material. 9. A step of evaporating a tellurium polyatomic molecule, a step of decomposing the tellurium polyatomic molecule to produce a molecule having a small number of atoms, and the step of mixing the tellurium molecule having a small number of atoms as a raw material. The method for producing a multicomponent mixed crystal according to claim 7, wherein the method comprises: 10. The method of manufacturing a mixed crystal according to claim 4, further comprising the step of simultaneously irradiating nitrogen plasma to produce a group 2-6 semiconductor layer to which nitrogen is added.
10. The method for producing a multicomponent mixed crystal according to any one of items 9 to 9. 11. The method according to claim 1, wherein the mixed crystal has a lattice matching with GaP.
eMgSSe mixed crystal, BeMgSS lattice matched to ZnS
11. The method for producing a multi-element mixed crystal according to claim 6, wherein the mixed crystal is e-mixed crystal, MgZnSSe mixed crystal lattice-matched to GaAs, or MgZnSSe mixed crystal lattice-matched to ZnSe. 12. The method according to claim 1, wherein the mixed crystal has a lattice matching with GaP.
eZnSTe mixed crystal, BeZnST lattice matched to ZnS
e mixed crystal, MgZnSTe mixed crystal lattice-matched to GaAs,
MgZnSTe mixed crystal lattice matched to InP, MgZnSTe mixed crystal lattice matched to InAs, MgZnSTe mixed crystal lattice matched to GaSb, Mg lattice matched to ZnSe
ZnSTe mixed crystal, MgZnSTe lattice matched to CdS
Mixed crystal, MgZnSTe mixed crystal lattice-matched to CdSe, Z
MgZnSTe mixed crystal lattice matched to nTe, MgCdSTe mixed crystal lattice matched to InP, MgCdSTe mixed crystal lattice matched to InAs, MgC lattice matched to GaSb
dSTe mixed crystal, MgCdSTe mixed crystal lattice-matched to CdS, MgCdSTe mixed crystal lattice-matched to CdSe or Z
The method for producing a multicomponent mixed crystal according to claim 7, wherein the mixed crystal is a MgCdSTe mixed crystal lattice-matched to nTe. 13. The mixed crystal is BeZnSeTe mixed crystal lattice-matched to GaAs, and BeZ is lattice-matched to ZnSe.
nSeTe mixed crystal, MgZnSeT lattice-matched to InP
e mixed crystal, MgZnSeTe mixed crystal lattice-matched to InAs, MgZnSeTe mixed crystal lattice-matched to GaSb, C
MgZnSeTe mixed crystal lattice matched to dS, MgZnSeTe mixed crystal lattice matched to CdSe, MgZnSeTe mixed crystal lattice matched to ZnTe, MgCdSeTe mixed crystal lattice matched to InAs, MgC lattice matched to GaSb
dSeTe mixed crystal, MgCdSe lattice-matched to CdSe
MgCdSeTe lattice-matched to Te mixed crystal or ZnTe
The method for producing a multicomponent mixed crystal according to claim 8, wherein the mixed crystal is a mixed crystal. 14. A compound containing only selenium as a Group 6 element.
In forming a Group 6 semiconductor mixed crystal, a step of converting nitrogen into plasma, a step of evaporating polyatomic molecules of selenium, and a step of decomposing the polyatomic molecules of selenium to produce molecules having a small number of atoms, The above 2-6, wherein nitrogen is added using the nitrogen plasma and the molecule having a small number of atoms of selenium as raw materials.
Producing a mixed semiconductor mixed crystal. 15. The semiconductor device according to claim 1, wherein the mixed crystal of Group 2-6 semiconductor is GaAs.
BeMgZnSe mixed crystal lattice matched to ZnSe, BeMgZnSe mixed crystal lattice matched to ZnSe, MgZnCdSe mixed crystal lattice matched to InP or MgZ lattice matched to CdS
The method of claim 14, wherein the mixed crystal is nCdSe mixed crystal. 16. heating the polyatomic molecule, irradiating with an electron beam,
The method for producing a multi-element mixed crystal according to any one of claims 1 to 15, wherein the method is decomposed or excited by any means selected from light irradiation, ion irradiation, and plasma conversion. 17. The method for producing a multi-element mixed crystal according to claim 1, wherein the multi-element mixed crystal is produced in a vacuum. 18. The multi-component mixed crystal according to claim 1, further comprising a step of producing the mixed crystal at a temperature at which the multi-component mixed crystal becomes immiscible in a thermal equilibrium state. Manufacturing method. 19. An optical semiconductor device using a multi-element mixed crystal film having no composition fluctuation manufactured by the manufacturing method according to claim 1. Description: 20. An electronic semiconductor device using a multi-component mixed crystal film having no composition fluctuation manufactured by the manufacturing method according to claim 1. Description: