JP3535876B2 - Semiconductor device and manufacturing method thereof - Google Patents

Abstract

PURPOSE:To obtain an interface of high reliability between an insulating film and a semiconductor, by forming an insulating film subjected to sintering process by using hydrogen active seeds which are not accompanied by plasma. CONSTITUTION:This semiconductor device is provided with insulating films 25, 26 subjected to sintering process by using hydrogen active seeds which are not accompanied by plasma. The hydrogen active seeds preferably formed by bringing hydrogen gas or hydrogen containing gas into contact with nickel or nickel containing material heated at 300 deg.C or higher. The insulating films 25, 26 are silicon oxide films, which are preferably turned into the gate oxide film, or the interlayer insulating film of MOS. For example, after oxide films are formed by thermal oxidation in silicide layers 21-24, N<+> regions 17, 18, P<+> regions 19, 20, a P<-> region 14 and an N<-> region 15 which are exposed in contact holes, the gate insulating films 25, 26 of a CMOS in a semiconductor device are formed by performing sintering process using hydrogen active seeds at 300 deg.C.

Description

Detailed Description of the Invention

[0001]

The present invention relates relates to a semiconductor device and a manufacturing <br/> how relates to a manufacturing method for a semiconductor device capable of particularly formed of high oxide film / silicon interface reliability.

[0002]

2. Description of the Related Art A conventional technique is to use an oxide film as an insulating film.
Silicon will be described as an example of the semiconductor.

Conventionally, the so-called sintering method is known as one of the techniques for terminating the dangling bond at the oxide film / silicon interface. In this method, after forming an oxide film or an oxide film and electrodes, wirings, etc. on a silicon substrate, hydrogen or a mixed hydrogen gas such as an inert gas is brought into contact with a heated oxide film / silicon substrate. This is a method of terminating dangling bonds at the oxide film / silicon interface with hydrogen.

Further, hydrogen gas or a mixed gas in which an inert gas and hydrogen gas are mixed is turned into plasma, and hydrogen ions and active hydrogen species in the plasma are brought into contact with the oxide film / silicon substrate to dangling bonds with hydrogen. A technique of terminating with is also known.

[0005]

However, in the former technique, since the introduced gas is not active, the dangling bond termination at the oxide film / silicon interface is insufficient and a highly reliable device is obtained. Not manufactured.

On the other hand, in the latter technique, since dangling bonds are terminated by using hydrogen active species in plasma, dangling bonds are sufficiently terminated and a device having high reliability can be obtained. Be expected. However, it has been found that when the dangling bond is actually terminated by the latter technique, a device having high reliability cannot always be obtained. In this way, the inventor
We have searched for the reason why a device with high reliability cannot be obtained contrary to expectations. As a result, in the latter technique, since plasma is generated, the plasma damages the oxide film and the oxide film / silicon interface, and as a result, new defects and dangling bonds are generated. It was clarified that it was the cause.

After all, at present, oxide films and oxide films /
There is no technology capable of sufficiently terminating dangling bonds without damaging the silicon interface, the oxide film / semiconductor interface has a low interface state, and a highly reliable semiconductor device has not been realized.

[0008]

The present invention has been made to solve the above-mentioned problems of the prior art and has a highly reliable interface between an insulating film and a semiconductor (for example, an oxide film / silicon interface). and to provide a semiconductor device and a manufacturing how.

[0009]

According to a method of manufacturing a semiconductor device of the present invention, in the method of manufacturing a semiconductor device having an insulating film / semiconductor interface, a hydrogen active species without plasma is brought into contact with the insulating film. It said by carrying out the ring
It characterized the this <br/> of terminating dangling bonds in the insulating film / semiconductor interface. The semiconductor device of the present invention is an insulating film / semiconductor
In a semiconductor device having a body surface, the insulating film by sintering process that by the activated hydrogen species without plasma
/ The dangling bond at the semiconductor interface is terminated .

[0010]

In the semiconductor device of the present invention, a hydrogen activated species (eg, 300 ° C. or higher) without plasma is added to the insulating film of the semiconductor device having an insulating film / semiconductor interface (eg, silicon oxide film / silicon interface). It is formed by bringing into contact with nickel or a material containing nickel heated to a temperature to generate hydrogen active species). Upon contact with the insulating film, the hydrogen active species diffuses in the insulating film and terminates dangling bonds in the insulating film and at the insulating film / semiconductor interface without damaging the dangling bonds. Therefore, a highly reliable insulating film and eventually a semiconductor device can be obtained.

[0011]

Examples of Embodiments Examples of embodiments of the present invention will be described below.

(Means for Generating Hydrogen Active Species) In the present invention, hydrogen active species are generated from hydrogen gas or a gas containing hydrogen gas without plasma and the dangling bond is terminated by using the hydrogen active species. Is one of the features. The means for generating such hydrogen active species (hydrogen active species generating means) may be configured as follows, for example.

For example, as shown in FIG. 3, the gas inlet 3
The gas introducing pipe 302 is connected to the furnace core pipe 301, and the heating means 309 is arranged so as to heat the gas introducing pipe 302. At that time, the inner surface of the gas introduction pipe 302 is made of nickel or a material containing nickel).

In this case, the gas introducing pipe 30 is heated by the heating means.
When the inside of 2 is heated to 300 ° C. or higher and hydrogen gas is introduced into the gas introduction pipe 302 from the hydrogen gas source, the gas introduction pipe 30
Active hydrogen species are generated from the hydrogen gas contacting the inner surface of 2. It is considered that this is because at the temperature of 300 ° C. or higher, nickel in the gas introducing pipe 302 or nickel in the material containing nickel has a catalytic action. Since the activated hydrogen species thus generated are naturally not accompanied by plasma, they do not damage the object to be treated.

Further, hydrogen gas may be replaced with another gas (for example, Ar.
(Inert gas such as
As shown in FIG. 4, the gas introduction pipe 302 having the branch pipes 302a and 302b is connected to the gas introduction port 312 and connected to the core tube 301. The branch pipe 302a is connected to the hydrogen gas source. The example shown in FIG. 4 is a case where there are two branch pipes, but two or more branch pipes may be provided if necessary.

Part or all of the inner surface of the introduction pipe 302 is made of nickel or a material containing nickel. In the example shown in FIG. 4, the inner surface of the branch pipe 302a is made of nickel or a material containing nickel. And the heating means 309 is arrange | positioned so that this branch pipe 302a can be heated. Of course, the part where the branch pipes 302a, 302b join (this part is the branch pipes 302a, 3b).
The heating means 309 may be arranged so as to be able to heat the gas mixing part 302c from 02b).

Although FIGS. 3 and 4 show an example in which the introducing pipe 302 is provided, such an introducing pipe is not provided, and as shown in FIG. 5, the inner surface of the core tube 301 is made of nickel or a material containing nickel. You may comprise.

In this case, it is not necessary to provide the heating means as shown in FIGS. 3 and 4, and the heating can be performed by the core tube heating means 304. Therefore, hydrogen active species are generated inside the core tube 301. Can be made. In addition, the part composed of nickel or a material containing nickel,
A substrate 305 on which a semiconductor device which is an object to be processed is formed
Although it is sufficient only on the upstream side of the position where
The balance may be made of such a material.

In the above-described embodiment, the inner surface of the introduction tube or the core tube is made of nickel or a material containing nickel to form the active hydrogen species generating means.
It may have a configuration other than this. For example, the activated hydrogen species generating means may be configured by providing a container filled with nickel (for example, fibrous nickel, reticulated nickel, sponge nickel, etc.) between the hydrogen gas source and the core tube. If hydrogen gas or a gas containing hydrogen gas is passed through this container and this container is heated to 300 ° C. or higher, hydrogen active species can be obtained, and this hydrogen active species can be introduced into the core tube. it can.

When the wiring portion of the semiconductor device is formed of nickel or a nickel alloy, the wiring portion is heated to 300 ° C. or higher, and hydrogen gas or a gas containing hydrogen gas is brought into contact with the wiring portion to generate hydrogen. Active species are generated.

(Nickel, Material Containing Nickel) Next, nickel or a material containing nickel will be described.

As the material containing nickel, for example, N
i-based alloys are preferred. In addition, among Ni-based alloys, Ni
A -Mo-based alloy or a Ni-W-based alloy is preferable. More specifically, for example, Hastelloy (registered trademark) can be mentioned.

Further, as another material containing nickel,
For example, stainless steel having a surface roughness of 1 μm or less and electrolytically polished may be used. In this case, it is more preferable to use a stainless steel surface on which a passivation film formed by heat treatment in an oxidizing atmosphere having an impurity concentration of 10 ppb or less is formed. Has a passivation film formed by heat treatment in an oxidizing atmosphere and then reduction treatment in a hydrogen atmosphere (Japanese Patent Application No. 3-2.
It is more preferable to use (provided separately in No. 12592). The surface of such a passivation film contains chromium oxide as a main component, and the surface thereof has excellent corrosion resistance, and since the adsorption of water is extremely small, the mixing of impurities into the gas can be extremely reduced. The surface roughness of the passivation film is preferably 0.5 μm or less, more preferably 0.1 μm or less. The passivation film contains chromium oxide as a main component, but contains nickel oxide. Nickel in the nickel oxide acts as a catalyst, and the hydrogen gas contacting the surface of the passivation film is removed. It is considered that hydrogen active species are generated.

(Insulating Film, Semiconductor) Examples of the semiconductor in the present invention include a semiconductor wafer, an insulating substrate, or a semiconductor layer formed on the semiconductor wafer.

Examples of the semiconductor layer include compound semiconductors such as silicon, germanium and GaAs.

The crystalline state of the semiconductor may be amorphous, polycrystalline or single crystal.

On the other hand, as the insulating film, for example, an oxide film,
An example is a nitride film. This insulating film may be formed by heating (for example, thermal oxide film), formed by deposition (deposited oxide film), or formed by any other method.

(Temperature of Nickel and Material Containing Nickel) The temperature of nickel and the material containing nickel is 300 ° C. or higher. If the temperature is less than 300 ° C, hydrogen active species are not sufficiently generated. Particularly, 300 ° C to 450 ° C is preferable and 300
More preferably, the temperature is from 400 ° C to 400 ° C. When the temperature exceeds 450 ° C, the amount of active hydrogen species generated increases. On the other hand, when a passive film is not formed on the surface of nickel or a material containing nickel, impurities are released from the surface,
This is because the impurities may be mixed in the gas.

(Treatment Temperature) In the present invention, the substrate temperature when the gas containing hydrogen active species is brought into contact with the substrate having the insulating film is 20.
-1200 degreeC is preferable, 20-600 degreeC is more preferable, 20-450 degreeC is further more preferable.

(Gas) In the present invention, the gas brought into contact with nickel or a material containing nickel is hydrogen gas or a gas containing hydrogen gas.
As the gas containing hydrogen gas, for example, a gas in which hydrogen gas and an inert gas (for example, Ar gas, nitrogen gas, etc.) are mixed may be used. The gas flow rate is not particularly limited.

[0031]

Embodiments of the present invention will be described below with reference to the drawings.

Example 1 FIG. 1 is a sectional view showing the basic structure of a semiconductor device according to this example.

Here, a pair of C included in the semiconductor device.
Only MOS is shown. In FIG. 1, 11 is an electrode on the back surface of the substrate, 1
1 is a p ⁺ substrate, 13 is a n ⁺ buried region, 14 is a high resistance p
^- regions, 15 high-resistivity n ^- region, 16 Zemmidori isolation region, 17 and 18 n ⁺ region, 19, 20 p ⁺ region, 2
1, 22, 23 and 24 are MoSi ₂ , WSi ₂ and TaSi
₂ , metal silicide such as TiSi ₂ or Pd ₂ Si,
Reference numerals 25 and 26 denote silicon oxide films (gate insulating films) that have been subjected to sintering processing, and the processing method thereof will be described in detail later. 27 and 28 are gate electrodes, 29, 30, and 31 are A
1, metal electrode such as AlSi or AlCu, 32, 3
3 and 34 are metal fluoride films for insulating and separating the electrodes 27, 28, 29, 30 and 31 (AlF ₃ when Al is used for the electrodes, for example), and 35 is P for passivation.
It is an SG film or a nitride film.

In FIG. 1, the interface between the gate insulating film 25 and the region 14 is formed closer to the region 14 than the interface between the regions 17 and 18 and the region 14, and the interface between the gate insulating film 26 and the region 15 is the regions 19 and 20. Is formed on the region 15 side from the interface between the region 15 and the region 15. In this structure, the electric field strength between the source and the drain of the channel portion is reduced, so that the short channel effect hardly occurs.

In FIG. 1, the material of the gate electrodes 27 and 28 is n.
It is desirable to have a high diffusion cell for both the ⁺ regions 17, 18 and p ⁺ regions 19, 20. For example, A
High diffusion potential can be obtained by using 1, AlSi or AlCu. Al has a diffusion potential of about 0.7 V for the n ⁺ region and about 0.4 V for the p ⁺ region. Of course, the gate electrode has a work function value of n ⁺
It may be a refractory metal or a metal silicide as long as it has a high barrier to both the region and the p ⁺ region. Therefore, the resistance of the gate electrode is small.

Further, in this structure, n ⁺ by拡撒potential of the p ⁺ substrate 12 and the gate electrode 27 to the source region, and p ⁺ n ⁺ buried region 13 to the source region
A potential barrier is generated in the channel by the diffusion potential of the gate electrode 28, and the normally-off characteristic of the MOS transistor is realized when the impurity density of the channel regions 14 and 15 is about 10 ¹⁴ to 10 ¹⁶ cm ⁻³ . That is, area 1
4 and 15 are high resistance regions, and the impurity concentration is kept low. Therefore, the channel width in which electrons and holes flow is kept wide, and a short channel can be realized without reducing the movement of carriers traveling in the channel. That is, the MOS transistor has a large conversion conductance of 8 m.

In FIG. 1, the junction surface between the n ⁺ region 17 and the region 14, the junction surface between the n ⁺ region 18 and the region 14, the junction surface between the p ⁺ region 19 and region 15, and the p ⁺ region 20 and the region. The joint surface with 15 is a flat surface, and since the area of the joint surface is small, the fringe effect is small and the capacitance between the source region and the drain region, between the source region and the substrate, and between the drain region and the substrate is small.

In FIG. 1, the materials of the electrodes 29, 30, 31 are, for example, Al, AlSi, AlCu, AlCuSi.
And the resistances of the source electrode and the drain electrode are small.
Since the source resistance, the drain resistance, and the gate resistance are small, the source and drain capacitances are small, and the conversion conductance g _m is large, the transistor has excellent high-speed performance. Of course, the source electrode and the drain electrode may be made of a metal such as Mo, W, Ta, or Ti.

In FIG. 1, an n ⁺ buried region 13 is used as a substrate.
Although the p ⁺ substrate 12 having the above has been described, the operation of the semiconductor device described above is performed by sapphire, spinel, quartz,
It can also be realized by using an absolutely insulative substrate such as AlN or SiC.

Next, FIG. 2 shows an example of a manufacturing process for manufacturing the semiconductor device of FIG. A case where a p ⁺ substrate is used as the substrate 12 will be described. In the region 13 of the p ⁺ substrate 12,
For example, by thermal diffusion of P from a PSG film deposited by the CVD method,
⁺ Form a buried region. Of course, the region 13 may be formed by ion implantation of P or As and activation anneal. The isolation region 16, the p ⁻ region 14, and the n ⁻ region 15 are formed as follows, for example. After thermally oxidizing the surface of the substrate 12 having the embedded region 13 for several tens of nm, a PSG film or a BPSG film is formed to a predetermined thickness by the CVD method.
The thermal oxide film and the PSG film or BPSG film corresponding to the regions 14 and 15 are removed by reactive ion etching. Then, SiH ₄ , Si ₂ H ₆ or S
The regions 14 and 15 are selectively epitaxially grown by the CVD method using iH ₂ Cl ₂ . Thus, FIG.
Although the structure shown in (a) is formed, the structure is not limited to the above method and may be formed by any other method. The region 14,
The thickness of 15 may be appropriately selected depending on the device to be manufactured, but for example, a value of about 0.03 to 0.5 μm may be selected.

Next, a metal layer having a thickness of 10 to 20 nm, for example, W, Ta, T is selectively formed on the surface of the regions 14 and 15.
A layer made of i, Mo, etc. is grown. After that, by ion implantation through these metal layers, for example, As is selectively implanted in the region 14 and, for example, B and Si are selectively implanted in the region 15, and then an activation anneal is performed.
As shown in (b), the silicide layers in the regions 21, 22, 23, 24 and the n ⁺ regions 17, 18 and the regions 19, 2
Form 0.

Next, by the sputtering method or the CVD method,
For example, an Al film having a thickness of about 0.2 to 1.0 μm is formed, and a predetermined region is etched by reactive ion etching as shown in FIG. Areas 29, 30,
The surface of 31 is, for example, 100 using ultra-pure F ₂ gas.
Fluorine at ℃ for 4 hours, then anneal at 150 ℃ for 5 hours in an inert gas (for example, N ₂ gas).
Insulating layer of AlF _{3 on} the surface of the region 1 (region 3 in FIG. 2D)
2, 33, 34) is formed. Next, as shown in FIG. 2D, using the regions 32, 33, and 34 as masks, predetermined regions of the metal silicide layer, the n ⁺ region, and the p ⁺ region are etched by reactive ion etching to form contact holes. Form.

Next, an oxide film is formed on the surface exposed from the contact hole by, for example, a thermal oxidation method. That is,
As shown in FIG. 2E, the silicide layer, the n ⁺ region, the p ⁺
An oxide film is formed in the region, n ⁻ region by thermal oxidation.

Next, the sintering process described below is performed. By the sintering process described below, the oxide film and the oxide film / silicon interface having a low number of dangling bonds in the oxide film and the oxide film / silicon interface and a low trap density are formed.

Further, the structure of the semiconductor device shown in FIG.
It can be formed by forming the gate electrodes 27 and 28, etching a predetermined region, forming the passivation layer 35, and forming the electrode 11.

FIG. 3 shows the sintering apparatus used in this embodiment.

The sintering apparatus in this example is a model single tube sintering furnace apparatus. In the following description, the same or equivalent components will be denoted by the same reference numerals.

As shown in FIG. 3, in the apparatus of this example,
The furnace core tube 301 has a gas introduction port 312 for introducing gas from the outside at one end side in the longitudinal direction of the core tube, and the gas introduction pipe 30 is communicated with the gas introduction port 312 on the outer side thereof.
Two are provided.

In this example, the gas introduction pipe 302 is made of a nickel alloy (Hastelloy C: registered trademark), and the heating source 9 as a heating means is installed outside the gas introduction pipe 302. .

The material of the gas introducing pipe 302 may be stainless steel, Hastelloy, etc. in addition to nickel steel.
That is, the material containing at least nickel metal may be used, and preferably the material may be surface-treated (for example, dry oxygen oxidation passivation treatment) so as not to contaminate the core tube 301. As described above, it has been confirmed that the same results as in this example can be obtained.

A gas supply system (not shown) is connected to the upstream side of the gas introduction pipe 302 via a valve. The heating source 309 may be composed of an electric resistance heater, an infrared lamp heater, or the like.

On the other hand, an object to be processed, for example, a silicon substrate 305 is placed on the quartz susceptor 306 which is a holding member in the furnace core tube 301, and the heating source 30 serving as the furnace core tube heating means.
It is designed to be heated by 4. The heating source 30
Reference numeral 4 includes, for example, an electric resistance heater, an infrared lamp heater, and the like. The materials of the core tube 301 and the susceptor 306 are synthetic quartz, fused quartz,
Alumina, silicon carbide, aluminum nitride, boron nitride and the like can be mentioned, and materials that do not contaminate the silicon substrate (for example, sodium ion free, heavy metal free, degassing free, particle free, etc.) are desirable.

A more specific example of sintering using the apparatus shown in FIG. 3 will be described below.

After forming the oxide film in the contact hole, the silicon substrate 305 is placed on the quartz susceptor 306, the lid 310 of the opening 311 of the furnace core tube 301 is opened, and the silicon substrate 305 is loaded into the furnace core tube 301 by soft landing transfer. Then, the lid 310 was closed. Then, the silicon substrate 305 was heated to 300 ° C. by the heating source 304.

A mixed gas of hydrogen gas and argon gas was introduced into the gas introduction pipe 302. In addition, this mixed gas is 1
It was a mixed gas of 0% hydrogen gas and argon gas, and the flow rate was set to 1000 cc / min.

A mixed gas of hydrogen gas and argon gas,
Gas introduction pipe 30 heated to 400 ° C. by a heating source 309
The inner surface of No. 2 was brought into contact with the inner surface of No. 2 to generate hydrogen active species, which was introduced into the furnace core tube 301 through the gas introduction port 312.

On the other hand, the silicon substrate 30 in the core tube 301
5 was heated to 300 ° C., the mixed gas was introduced into the furnace core tube 301, and then the mixture was held at 300 ° C. for 30 minutes to perform sintering treatment. The mixed gas containing active hydrogen species introduced from the gas inlet 312 was brought into contact with the surface of the silicon substrate 305, diffused in the oxide film, and terminated dangling bonds in the oxide film and at the oxide film / silicon interface.

After the sintering process, the silicon substrate 305 and the quartz susceptor 306 were carried out from the furnace core tube 301 by the reverse procedure of the soft landing transfer.

After that, the interface state density of the MOS diode on the silicon substrate 305 after the sintering process was measured by quasi-constant capacitance-voltage measurement. As an example of actual measurement, the result was obtained that the interface-level density after sintering was 2 × 10 ⁹ cm ⁻² eV ⁻¹ or less.

Comparative Example On the other hand, except that the gas introduction pipe 302 is not heated and active hydrogen is not produced, the other steps are performed under the same conditions as described above.
That is, when the setting of the silicon substrate 305 on the quartz susceptor 306, the soft landing transfer, the heating of the silicon substrate 305 in a hydrogen / argon mixed gas for 30 minutes at 300 ° C., and the removal by the soft landing transfer were performed under the same conditions, The interface state density of the MOS diode on the silicon substrate 305 was 1 × 10 ¹⁰ cm ^-2 eV ^-1 .

The interface state density of the oxide film / silicon interface in the embodiment of the present invention is 2 × 10 ⁹ cm ⁻² e as described above.
Since it is V ⁻¹ or less, it can be seen by comparing the two that the number of dangling bonds at the oxide film / silicon interface is reduced in the example of the present invention. [0062] After all, referring to FIG. 1, the silicon oxide film (gate oxide film) 25,
Since 26 is subjected to sintering treatment with active hydrogen species that does not accompany plasma, the neutral trap density in the oxide film is low. Even if hot electrons are injected into the oxide film during device operation, the threshold voltage shift amount is small and the transistor has excellent reliability. In addition, an oxide film / sintered by hydrogen active species without plasma
There are few dangling bonds at the silicon interface,
Moreover, the bonding force between silicon atoms and hydrogen atoms in the oxide film and the oxide film / silicon interface is strong. Even when hot electrons are injected into the oxide film during device operation, the bond between silicon atoms and hydrogen atoms is not broken, and traps in the oxide film or interface levels at the oxide film / silicon interface are not generated. It does not deteriorate, has excellent reliability performance,
It becomes a transistor that maintains ultra-high speed performance.

As described above, the semiconductor device having the structure including the oxide film formed according to the present invention can realize a semiconductor integrated circuit using an insulated gate transistor having excellent ultra-high speed and excellent reliability.

Example 2 In Example 2, the device shown in FIG. 4 was used. This device
Mixing part 30 of hydrogen gas or active hydrogen species and argon gas
2c is provided in the gas introduction pipe 302. That is, in this example, the branch pipes 302a, 302a are used as the gas introduction pipes.
A gas introduction pipe 302 having 02b was used. Branch pipe 30
The portion where the 2a and 302b join together is the gas mixing section 302c.
Becomes In this example, the branch pipe 302a is connected to a hydrogen gas source (not shown), and the branch pipe 302b is connected to an argon gas source (not shown). Further, in this example, the heating means 309 is provided near the branch pipe 302a. Of course, it may be provided near the mixing section 302c as described above.

This embodiment is substantially the same in construction and operation as the above-mentioned Embodiment 1 except that the gas mixing section is provided in the gas introduction pipe.

That is, in the case of the present embodiment, the above-mentioned first embodiment
Silicon substrate 30 taken out from core tube 301
The interface state density of the MOS diode on 5 is 2 × 10 ⁹ c
It was m ^-2 eV ^-1 or less.

Example 3 In Example 3, the device shown in FIG. 5 was used. In this apparatus, the core tube 301 is made of nickel metal.

The heating source 304 heats the silicon substrate, which is the heated portion, via the furnace tube 301.

The mixed gas of hydrogen and argon as the introduction gas flowing in the gas introduction pipe 302 is set to a flow rate of, for example, 1000 cc / min, but it is not possible to come into contact with the heated nickel metal while being introduced into the core tube 301. Absent. In the case of this embodiment, the interface state density of the MOS diode on the silicon substrate 305 taken out from the core tube after the reaction process is 2
It was not more than × 10 ⁹ cm ^-2 eV ^-1 .

The structure is substantially the same as that of the first, second, and third embodiments except that the structure is vertical, and the operation is the same as that of the first embodiment. . That is, the interface state density of the MOS diode on the silicon substrate 305 taken out from the core tube 301 was 2 × 10 ⁹ cm ^-2 eV ^-1 or less as in the above-mentioned embodiment.

FIG. 6 shows an M formed by the apparatus according to the first embodiment.
It is a graph which shows the hot electron tolerance of MOSFET formed with OSFET and the conventional device. The horizontal axis of FIG. 6 represents the number of injected hot electrons, and the vertical axis represents the shift amount of the threshold voltage. Thickness of oxide film is 10n
m. N ⁺ type polycrystalline silicon is used as the gate electrode.

MOSFE formed by the device according to the first embodiment
T has a small shift amount of the threshold voltage of 0.03 V even when 1 × 10 ¹⁷ hot electrons are injected. On the other hand, the MOSFET formed by the conventional device has a large threshold voltage shift of 0.2V. That is, Example 1
It has been found that the MOSFET formed by the device according to (1) exhibits high reliability.

FIG. 7 shows an M formed by the apparatus according to the first embodiment.
MOSFET formed by OSFET type TFT and conventional device
6 is a graph showing a sub-threshold characteristic of a T-type TFT. The horizontal axis of FIG. 7 represents the gate voltage, and the horizontal axis represents the drain current. As a substrate, an oxide film is formed on a silicon wafer, and p-type polycrystalline silicon is formed on the oxide film. The MOSFET is formed on polycrystalline silicon. The polycrystalline silicon is formed on the glass in addition to the oxide film. N ⁺ type polycrystalline silicon is used as the gate electrode. The channel length of the MOSFET is 2 μm and the channel width is 100 μm. As the drain voltage, 5V is applied.

The MOSFET type TFT formed in Example 1 has a drain current of 1 × 1 when the gate voltage is 0V.
It is 0 ^-13 A or less. On the other hand, the MO formed by the conventional device
SFET type TFT has 1 × 10 ⁻⁷ even if the gate voltage is 0V.
A current of A or higher is flowing. In the MOSFET TFT formed by the device of this embodiment, the dangling bond at the gate oxide film / polycrystalline silicon interface is terminated with hydrogen, and the dangling bond at the grain boundary of polycrystalline silicon forming the channel is terminated with hydrogen. Therefore, the drain current can be reduced. Therefore, the subthreshold characteristic of the MOSFET TFT formed by the device according to the first embodiment is improved. That is, it was found that the MOSFET TFT according to Example 1 exhibits high performance and high reliability.

The same results as those shown in FIGS. 6 and 7 were obtained in the devices according to the second and third embodiments.

It is to be noted that the insulating film in the semiconductor device of the present invention is effective even if it is processed in any step as long as it is a step after the film is formed. For example, it is effective that the sintering process is performed after forming the passivation layer 35. Especially after forming the oxide film,
When the silicon substrate is exposed to an electron beam and plasma to form a fine pattern, the oxide film or the oxide film / silicon interface is damaged and a neutral trap is generated. The neutral traps do not disappear when treated by the conventional sintering method, but the neutral traps disappear and the damage is recovered in the case where sintering is performed by hydrogen active species without plasma.

Although the single crystal silicon surface has been mainly described above, the present invention can be applied not only to the single crystal silicon surface but also to any crystalline silicon surface such as a polycrystalline silicon surface and an amorphous silicon surface. For example, in the manufacture of a TFT transistor, in the case of an oxide film / polycrystalline silicon substrate, neutral traps in the oxide film and the interface states at the oxide film / silicon interface have disappeared, and the grain boundary level in the polycrystalline silicon has also disappeared. The position also disappears, and a highly reliable and high performance TFT transistor can be realized.

In the manufacture of a semiconductor device having nickel or a nickel alloy in a part of the semiconductor device, a substrate having nickel or a nickel alloy is heated to a temperature of 300 ° C. or higher to generate hydrogen gas or hydrogen gas and an inert gas. By bringing the mixed gas into contact, the same effect as that of the method of the present invention can be realized. For example, when the electrodes 29, 30, 31 of the semiconductor device shown in FIG. 1 are made of nickel or nickel alloy, after forming the gate oxide films 25, 26, by heating to a temperature of 300 ° C. or higher by the conventional sintering method. By eliminating the traps in the oxide film and the interface states at the oxide film / silicon interface, it is possible to realize a semiconductor device having excellent reliability.

[0079]

According to the present invention, it is possible to realize a highly reliable semiconductor device which is ultra-miniaturized.

[Brief description of drawings]

FIG. 1 is a sectional structural view of a semiconductor device according to an embodiment of the present invention.

FIG. 2 is a cross-sectional view showing a manufacturing process of a semiconductor device of the present invention.

3 is a schematic configuration diagram of a heat treatment apparatus used in Example 1. FIG.

FIG. 4 is a schematic configuration diagram of a heat treatment apparatus used in Example 2.

FIG. 5 is a schematic configuration diagram of a heat treatment apparatus used in Example 3.

FIG. 6 is a graph showing hot electron resistance of the MOSFET formed in Example 1 and the MOSFET formed by the conventional technique.

7 is a MOSFET type TF formed in Example 1. FIG.
7 is a graph showing subthreshold characteristics of a T-transistor and a MOSFET TFT transistor formed by a conventional technique.

[Explanation of symbols]

11 electrode on substrate surface, 12 p ⁺ substrate, 13
n ⁺ buried region, 14 high resistance region, 15
High resistivity n ⁻ region, 16 insulating isolation region, 1
7,18 n ⁺ regions, 19,20 p ⁺ regions, 21,2
2, 23, 24 metal silicide, 25.26 silicon oxide film (gate insulating film), 27, 28 gate electrode,
29, 30, 31 metal electrode, 32, 33, 34 metal fluoride (AlF ₃ ), 35 PSG film, nitride film, 301 core tube, 302 gas introduction tube, 3
02a branch pipe, 302b branch pipe, 302c
Mixing part, 304 Core tube heating means (heating source), 30
5 Heating means (heating source) for heating the silicon substrate (object to be processed), 306 susceptor, 307 valve, 309 gas introduction pipe.

Claims (21)

(57) [Claims] 1. A method of manufacturing a semiconductor device having an insulating film / semiconductor interface, the insulating film, by performing the sintering by contacting the hydrogen active species without plasma
Terminate the dangling bond at the insulating film / semiconductor interface
Semiconductor manufacturing method, characterized in that that. 2. The activated hydrogen species without plasma is
2. The method for manufacturing a semiconductor device according to claim 1, wherein hydrogen gas or a gas containing hydrogen gas is brought into contact with nickel or a material containing nickel heated to a temperature of 300.degree. 3. The method of manufacturing a semiconductor device according to claim 2, wherein the gas containing hydrogen gas is a mixed gas of hydrogen and an inert gas. 4. The method of manufacturing a semiconductor device according to claim 3, wherein the inert gas is nitrogen, argon, or a mixed gas thereof. 5. The method of manufacturing a semiconductor device according to claim 1, wherein the insulating film is heated at a temperature of 20 to 1200 ° C. 6. The method of manufacturing a semiconductor device according to claim 5, wherein the insulating film is heated at a temperature of 20 to 600 ° C. 7. The method of manufacturing a semiconductor device according to claim 6, wherein the insulating film is heated at a temperature of 20 to 450 ° C. 8. The method of manufacturing a semiconductor device according to claim 1, wherein the insulating film is a silicon oxide film. 9. The method for manufacturing a semiconductor device according to claim 8, wherein the silicon oxide film is a thermally oxidized silicon oxide film, a deposited silicon oxide film, or a film obtained by nitriding these films. 10. The manufacturing of a semiconductor device according to claim 1, wherein the semiconductor is a silicon wafer or an insulating substrate or a silicon layer formed on the silicon wafer. Method. 11. The method of manufacturing a semiconductor device according to claim 10, wherein the silicon layer is an amorphous silicon layer, a polycrystalline silicon layer, or a single crystal silicon layer. 12. A wiring part of a semiconductor device is formed of nickel or a nickel alloy, and hydrogen active species is generated by bringing hydrogen gas or a gas containing hydrogen gas into contact with the wiring part. A method for manufacturing a semiconductor device as described above. 13. A semiconductor device having an insulating film / semiconductor interface.
In location, Danguri of the insulating film / semiconductor interface by by that thin <br/> Taringu process hydrogen active species without plasma
A semiconductor device characterized in that the bonding bond is terminated . 14. The activated hydrogen species is characterized by a gas containing hydrogen gas or hydrogen gas, in which was generated tighten into contact with materials containing nickel or nickel was heated to 300 ° C. over a temperature The semiconductor device according to claim 13. 15. The insulating film is a silicon oxide film,
15. The semiconductor device according to claim 13, wherein the silicon oxide film is a MOS gate insulating film. 16. The insulating film is a silicon oxide film,
15. The semiconductor device according to claim 13, wherein the silicon oxide film is a MOS interlayer insulating film. 17. The insulating film is a silicon oxide film,
15. The semiconductor device according to claim 13 or 14, wherein the silicon oxide film is an insulating film that insulates and separates a MOS gate electrode and a source or drain electrode. 18. The semiconductor in a semiconductor device is silicon
Formed on wafer or insulating substrate or silicon wafer
14. The silicon layer as described above.
18. The semiconductor device according to any one of items 17 to 17. 19. with the silicon oxide film, silicon wafer
C or the interface state density with the silicon layer is 2 × 10 ⁹ cm
^-2 eV ^-1 or less, The semiconductor device of Claim 18 characterized by the above-mentioned. 20. The silicon oxide film is a thermally oxidized silicon.
The semiconductor device according to any one of claims 13 to claims 1-9, characterized in that a phosphate of film or deposited silicon oxide film or a film which has been treated these nitride. 21. The semiconductor device according to claim 18, wherein the silicon layer is an amorphous silicon layer, a polycrystalline silicon layer or a single crystal silicon layer.