JP4285337B2 - Method for producing gallium nitride compound semiconductor wafer - Google Patents

Description

The present invention relates to a method for producing a gallium nitride compound semiconductor wafer used for light emitting devices such as ultraviolet, blue light emitting laser diode, ultraviolet, blue light emitting diode and the like.

Blue light-emitting elements have been studied using II-VI group ZnSe, IV-IV group SiC, III-V group GaN, and the like. Recently, among them, gallium nitride compound semiconductors [In _x Al _Y Ga _{1 -xYN} (0.ltoreq.X, 0.ltoreq.Y, X + _Y.ltoreq.1 )] exhibits a relatively excellent light emission at room temperature and has attracted attention. The blue light-emitting element having the nitride semiconductor basically has a general formula of In _X Al _Y Ga _1-XY N (0 ≦ X, 0 ≦ Y, X + Y ≦ 1) on a substrate made of sapphire. The represented nitride semiconductor epitaxial layer has a structure in which n-type and i-type or p-type layers are sequentially stacked.

  As a method for stacking nitride semiconductors, vapor phase growth methods such as an organic metal compound vapor phase growth method (hereinafter referred to as MOCVD method) and a molecular beam epitaxy method (hereinafter referred to as MBE method) are well known. For example, a method using the MOCVD method will be briefly described. In this method, an organic metal compound gas {trimethylgallium (TMG), trimethylaluminum (TMA), ammonia, etc.} is used as a reaction gas in a reaction vessel provided with a sapphire substrate. The crystal growth temperature is maintained at a high temperature of approximately 900 ° C. to 1100 ° C. to grow a nitride semiconductor on the substrate, and another impurity gas is supplied as necessary to make the nitride semiconductor an n-type. , I-type or p-type. In addition to sapphire, the substrate includes SiC, Si, etc., but sapphire is generally used. As n-type impurities, Si, Ge, Sn (however, in the case of a nitride semiconductor, there is a property of becoming n-type without doping n-type impurities), p-type impurities are Zn, Cd, Be, Mg, Ca, Ba and the like can be mentioned, among which Mg and Zn are most well known.

  In addition, as one method of forming a nitride semiconductor by MOCVD, if a nitride semiconductor is grown directly on a sapphire substrate at a high temperature, its surface state and crystallinity will be significantly deteriorated. First, it has been clarified that the crystallinity is remarkably improved by forming a buffer layer made of AlN at a low temperature of about 600 ° C. and subsequently growing the buffer layer on the buffer layer at a high temperature (Japanese Patent Laid-Open No. 2-247676). In addition, in the Japanese Patent Application No. 3-89840, the present inventor has shown that a crystalline nitride semiconductor can be stacked by using GaN as a buffer layer better than the conventional method using AlN as a buffer layer.

However, blue light emitting devices having nitride semiconductors have not yet been put into practical use. This is because a nitride semiconductor cannot be made into a p-type having a low resistance, and thus light emitting elements having a number of structures such as double hetero and single hetero cannot be formed. Even if a nitride semiconductor doped with a p-type impurity is grown by vapor phase epitaxy, the resulting nitride semiconductor does not become p-type and has a high resistance semi-insulating material with a resistivity of 10 ⁸ Ω · cm or more. That is, the actual situation was i-type. For this reason, the structure of the blue light-emitting element is currently known only to have a so-called MIS structure in which a buffer layer, an n-type layer, and an i-type layer are sequentially stacked on a substrate.

  In JP-A-2-257679, as a means for reducing the resistance of a high-resistance i-type and bringing it closer to the p-type, a high-resistance i-type gallium nitride compound semiconductor doped with Mg as a p-type impurity is formed in the uppermost layer. Later, a technique for reducing the resistance of a layer of about 0.5 μm from the surface by irradiating the surface with an electron beam having an acceleration voltage of 6 kV to 30 kV is disclosed. However, with this method, only the penetration depth of the electron beam, that is, only the extreme surface can be reduced in resistance, and the entire wafer must be irradiated while scanning the electron beam, so that the resistance cannot be reduced uniformly in the plane. there were.

Accordingly, an object of the present invention is to make a nitride semiconductor doped with a p-type impurity a p-type having a low resistance, and further, the resistance value is uniform over the entire wafer regardless of the film thickness. The present invention provides a method for manufacturing a gallium nitride compound semiconductor wafer having a pn junction that can have a possible structure.

The method for producing a gallium nitride compound semiconductor wafer of the present invention grows at least an n-type gallium nitride compound semiconductor layer and a gallium nitride compound semiconductor layer doped with a p-type impurity on a substrate by vapor phase growth. After that, a cap layer made of a stable material at 400 ° C. or more is further formed thereon, and annealing is performed to remove hydrogen from the gallium nitride compound semiconductor layer doped with the p-type impurity. The doped gallium nitride compound semiconductor is uniformly formed as a p-type gallium nitride compound semiconductor wafer over the entire surface .
Annealing the grown n-type gallium nitride compound semiconductor layer and the entire gallium nitride compound semiconductor layer containing p-type impurities in an atmosphere pressurized above the decomposition pressure of the gallium nitride compound semiconductor at that temperature The p-type gallium nitride compound semiconductor layer has a low resistance uniformly in the depth direction by releasing hydrogen bonded to the p-type impurity from the gallium nitride compound semiconductor layer containing the p-type impurity by thermally dissociating hydrogen It can be.

Annealing (annealing: heat treatment) may be performed in a reaction vessel after growing a gallium nitride compound semiconductor layer doped with a p-type impurity, or the wafer is taken out of the reaction vessel and used in an annealing apparatus. May be. The annealing atmosphere is performed in a vacuum, an inert gas such as N ₂ , He, Ne, or Ar, or a mixed gas atmosphere thereof, preferably nitrogen pressurized at a pressure higher than the decomposition pressure of the gallium nitride compound semiconductor at the annealing temperature Perform in an atmosphere. This is because pressurizing as a nitrogen atmosphere has an effect of preventing N in the gallium nitride compound semiconductor from decomposing and exiting during annealing.

  For example, in the case of GaN, the decomposition pressure of GaN is about 0.01 atm at 800 ° C., about 1 atm at 1000 ° C., and about 10 atm at 1100 ° C. For this reason, when annealing a gallium nitride compound semiconductor at 400 ° C. or higher, the gallium nitride compound semiconductor is more or less decomposed and its crystallinity tends to deteriorate. Therefore, decomposition can be prevented by pressurizing with nitrogen as described above.

  The annealing temperature is, for example, 400 ° C. or higher, preferably 700 ° C. or higher, and held for 1 minute or longer, preferably 10 minutes or longer. Even if it is performed at 1000 ° C. or higher, decomposition can be prevented by pressurizing with nitrogen as described above, and a p-type gallium nitride compound semiconductor having excellent crystallinity can be obtained stably as described later. .

  Further, as a means for suppressing decomposition of the gallium nitride compound semiconductor during annealing, a cap layer is further formed on the gallium nitride compound semiconductor layer doped with the p-type impurity, and then annealing is performed. The cap layer, that is, a protective film, is formed on a gallium nitride compound semiconductor doped with a p-type impurity, and then annealed at 400 ° C. or higher to reduce the pressure. Even under normal pressure, a low resistance p-type can be obtained without decomposing the gallium nitride compound semiconductor.

In order to form the cap layer, after forming a gallium nitride compound semiconductor layer doped with a p-type impurity, it may be subsequently formed in a reaction vessel, or the wafer is taken out of the reaction vessel and another crystal is formed. You may form with a growth apparatus, for example, a plasma CVD apparatus. The material of the cap layer may be any material that can be formed on a gallium nitride compound semiconductor and is stable at 400 ° C. or higher, and preferably Ga _x Al _1-X N (where 0 ≦ _{X ≦ 1), Si 3 N} 4, SiO 2 can be cited, appropriately selecting the type of the material by annealing temperature. The cap layer is usually formed with a thickness of 0.01 to 5 μm. If the thickness is less than 0.01 μm, the effect as a protective film cannot be sufficiently obtained. If the thickness is more than 5 μm, it takes time to remove the cap layer by etching after annealing and expose the p-type gallium nitride compound semiconductor layer. Therefore, it is not economical.

The present invention achieves the following excellent features.
(1) A gallium nitride compound semiconductor layer that has been extremely difficult to form into a low-resistance p-type layer even if doped with a p-type impurity until now is annealed into a low-resistance p-type gallium nitride compound semiconductor. it can. For this reason, when annealing, the hydrogen removed from the gallium nitride compound semiconductor layer containing the p-type impurity can be quickly removed. This is because hydrogen removed from the gallium nitride compound semiconductor layer containing the p-type impurity is removed without passing through the substrate and the n-type gallium nitride compound semiconductor layer.
In the present invention, an n-type gallium nitride compound semiconductor layer and a gallium nitride compound semiconductor layer doped with a p-type impurity are grown on a substrate and then annealed. The p-type layer is advantageous in that mass production of gallium nitride compound semiconductor light emitting devices having excellent light emission characteristics can be achieved at extremely low cost.
(2) The present invention is characterized in that the entire surface of a gallium nitride compound semiconductor layer containing p-type impurities can be uniformly and efficiently converted to p-type. In annealing the gallium nitride compound semiconductor layer containing the p-type impurity, the layer body is uniformly heated to be p-type.
The ability to uniformly convert the entire gallium nitride compound semiconductor layer containing p-type impurities into p-type is extremely important when manufacturing a semiconductor wafer. The gallium nitride compound semiconductor light emitting device is a large wafer, and is cut into small pieces to produce a chip of the gallium nitride compound semiconductor light emitting device so that the gallium nitride compound semiconductor layer is uniformly p-type. Otherwise, the yield of manufactured chips will be significantly reduced.
(3) The gallium nitride compound semiconductor layer containing the p-type impurity is deeply p-typed to be more uniformly p-type as a whole, thereby realizing excellent light emission characteristics.
On the other hand, a conventional gallium nitride compound semiconductor light emitting device in which a semiconductor layer containing a p-type impurity is converted to a p-type by an electron beam has a semiconductor layer containing a p-type impurity as the uppermost layer, and its extreme surface. However, the p-type has not been reduced in resistance. This is because the accelerated electron beam cannot be driven deeply.
In the present invention, since the entire gallium nitride compound semiconductor layer containing the p-type impurity is heated to p-type by annealing, the entire gallium nitride compound semiconductor layer containing the p-type impurity is heated. It is possible to realize a light emitting element that is more uniformly p-type and extremely bright.

Action

  FIG. 1 is a diagram showing that a gallium nitride compound semiconductor layer doped with a p-type impurity is changed to a low-resistance p-type by annealing. In this figure, however, the MOCVD method is used to first form a GaN buffer layer on a sapphire substrate, and then form a GaN layer with a film thickness of 4 μm while doping Mg as a p-type impurity on the sapphire substrate. FIG. 5 is a diagram in which after taking out and annealing in a nitrogen atmosphere while changing the temperature for 10 minutes, hole measurement of the wafer was performed, and resistivity was plotted as a function of annealing temperature.

As can be seen from this figure, when the annealing time is set to 10 minutes, the resistivity of the Mg-doped GaN layer suddenly decreases from around 400 ° C., and the P-type has a substantially constant low resistance from 700 ° C. or higher. The characteristic is shown and the effect of annealing appears. As a result of hole measurement of the GaN layer not annealed and the GaN layer annealed at 700 ° C. or more, the resistivity of the GaN layer before annealing was 2 × 10 ⁵ Ω · cm and the hole carrier concentration was 8 × 10 ¹⁰ / cm ³ . In contrast, the annealed GaN layer had a resistivity of 2 Ω · cm and a hole carrier concentration of 2 × 10 ¹⁷ / cm ³ .

Further, the 4 μm GaN layer annealed at 700 ° C. was etched to a thickness of 2 μm, and hole measurement was performed. As a result, the hole carrier concentration was 2 × 10 ¹⁷ / cm ³ and the resistivity was ³ Ω · cm. And almost the same value. In other words, the GaN layer doped with the P-type impurity has been p-type with low resistance over the entire region uniformly in the depth direction by annealing.

  Also, FIG. 2 shows that the MOCVD method is used, and a wafer in which a GaN buffer layer and a 4 μm GaN layer doped with Mg are formed on a sapphire substrate is annealed in a nitrogen atmosphere at 1000 ° C. for 20 minutes. The p-type GaN layers of the wafer (a) performed under atmospheric pressure and the wafer (b) performed at atmospheric pressure are irradiated with He—Cd laser as an excitation light source, respectively, and the crystallinity is compared with the photoluminescence intensity. It can be evaluated that the higher the blue emission intensity at 450 nm of the photoluminescence, the better the crystallinity.

  As shown in FIG. 2, when annealing is performed at a high temperature of 1000 ° C. or higher, the GaN layer tends to be thermally decomposed, so that its crystallinity tends to be deteriorated. A crystalline p-type GaN layer is obtained.

  FIG. 3 also shows a wafer (c) in which a GaN buffer layer and a 4 μm GaN layer doped with Mg are formed on a sapphire substrate, and an AlN layer as a cap layer is further grown thereon to a thickness of 0.5 μm. The annealed wafer (d) is now subjected to annealing at 1000 ° C. in a nitrogen atmosphere at atmospheric pressure for 20 minutes, and then the crystallinity of the p-type GaN layer exposed by removing the cap layer by etching is determined. It is a figure similarly shown in comparison with photoluminescence intensity.

  As shown in FIG. 3, the p-type GaN layer (c) that has been annealed without growing the cap layer undergoes decomposition at a high temperature, so that the decomposition of the p-type GaN layer proceeds, and the emission intensity at 450 nm becomes weak. End up. However, by growing the cap layer (in this case, AlN), the AlN of the cap layer is decomposed but the p-type GaN layer is not decomposed, so that the emission intensity remains strong.

  The reason why a low-resistance p-type gallium nitride compound semiconductor can be obtained by annealing is presumed as follows.

That is, in the growth of the gallium nitride compound semiconductor layer, NH ₃ is generally used as the N source, and it is considered that this NH ₃ is decomposed during the growth to generate atomic hydrogen. It is considered that this atomic hydrogen is bonded to Mg, Zn, etc. doped as acceptor impurities, thereby preventing p-type impurities such as Mg, Zn from acting as acceptors. For this reason, the gallium nitride compound semiconductor doped with the p-type impurity after the reaction exhibits high resistance.

However, by annealing after the growth, hydrogen bonded in the form of Mg—H, Zn—H, etc. is thermally dissociated and leaves the gallium nitride compound semiconductor layer doped with p-type impurities. Since p-type impurities normally function as acceptors, a low-resistance p-type gallium nitride compound semiconductor can be obtained. Therefore, it is not preferable to use a gas containing hydrogen atoms such as NH ₃ and H ₂ in the annealing atmosphere. Also, in the cap layer, it is not preferable to use a material containing hydrogen atoms for the above reasons. In the present invention, hydrogen removed from a gallium nitride compound semiconductor containing a p-type impurity does not necessarily remove all hydrogen but also removes part of hydrogen. Needless to say, it is within the range.

Hereinafter, the present invention will be described in detail with reference to examples. However, the following Reference Example 1 illustrates the manufacture of a light emitting device without a cap layer, but the cap layer is provided by the method shown in [0012] and [0013] on the light emitting device manufactured in this Reference Example. Can do.
[ Reference Example 1]
First, a well-washed sapphire substrate is placed on the susceptor in the reaction vessel. After evacuating the inside of the container, the substrate is heated at 1050 ° C. for 20 minutes while flowing hydrogen gas to remove oxides on the surface. Thereafter, the temperature was cooled to 510 ° C., and at 510 ° C., TMG gas as a Ga source was 27 × 10 ⁻⁶ mol / min, ammonia gas as an N source was 4.0 liter / min, and hydrogen gas was used as a carrier gas. A GaN buffer layer is grown to a thickness of 200 Å while flowing at 0 liter / min.

Next, after stopping only TMG gas and raising the temperature to 1030 ° C., TMG gas was again 54 × 10 ⁻⁶ mol / min, and SiH ₄ (monosilane) gas was newly added to 2.2 × 10 ⁻¹⁰ mol. The n-type GaN layer doped with Si is grown to a thickness of 4 μm by growing for 60 minutes while flowing at a rate of / min.

Subsequently, the SiH4 gas is stopped, and the Mg-doped GaN layer is grown to a thickness of 2.0 μm by growing for 30 minutes while flowing Cp ₂ Mg gas at 3.6 × 10 ⁻⁶ mol / min.

After stopping TMG gas and Cp ₂ Mg gas and flowing hydrogen gas and ammonia gas and cooling to room temperature, the gas flowing in the reaction vessel is replaced with nitrogen gas, and the temperature in the reaction vessel is changed to 1000 while flowing nitrogen gas. The temperature is raised to 0 ° C. and kept in the reaction vessel for 20 minutes for annealing.

  When the device thus obtained was made to emit light as a light emitting diode, it showed blue light emission having an emission peak near 430 nm, the light emission output was 50 μW at 20 mA, and the forward voltage was also 4 V at 20 mA. Further, when an element having a similar structure was fabricated without performing annealing and a light emitting diode was formed, the light emitted slightly yellow at 20 mA, and the diode was immediately broken.

The figure which shows the relationship between the annealing temperature and resistivity which concern on one Example of this invention. The figure which compares the crystallinity of the p-type GaN layer which concerns on one Example of this invention with photoluminescence intensity | strength. The figure which compares the crystallinity of the p-type GaN layer which concerns on one Example of this invention with photoluminescence intensity | strength.

Claims (3)

After growing at least an n-type gallium nitride compound semiconductor layer and a p-type impurity-doped gallium nitride compound semiconductor layer on a substrate by vapor phase growth, it is further stable at 400 ° C. or higher. A cap layer made of a material is formed, annealed to remove hydrogen from the gallium nitride compound semiconductor layer doped with the p-type impurity, and the gallium nitride compound semiconductor doped with the p-type impurity is made uniform over the entire surface. A method of manufacturing a gallium nitride compound semiconductor wafer which is a p-type gallium nitride compound semiconductor. 2. The method for producing a gallium nitride compound semiconductor wafer according to claim 1, wherein the cap layer has a thickness of 0.01 to 5 μm. 2. The method for producing a gallium nitride compound semiconductor wafer according to claim 1, wherein the annealing is performed at 400 ° C. or higher.

Images