JPH1081504A - Amorphous material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an optically active and inexpensive amorphous material improved in defect of amorphous compound semiconductors of the groups III to IV, having excellent photoconductive characteristics and high-speed responsiveness, hardly causing change with time and having environment-resistant characteristics and high temperature resistance. SOLUTION: This amorphous material comprises at least hydrogen, III group element in the periodic table, preferably gallium and nitrogen. In this case, in infrared ray absorption spectrum of the amorphous material, a ratio IN- H/IC- H of absorbance of an absorption peak (N-H) exhibiting bond between nitrogen and hydrogen to an absorption peak (C-H) exhibiting bond between carbon and hydrogen is >=2 and a ratio IN- H/IIII- H of an absorption peak (N-H) exhibiting bond between nitrogen and hydrogen of infrared ray absorption spectrum to an absorption peak (III-H) exhibiting bond between (N-H) and III group element is >=0.2. An organometallic compound containing a III group element is preferably used as a raw material for III group element and nitrogen gas is preferably used as a raw material for nitrogen.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optical semiconductor for optoelectronics, and more particularly to a novel and excellent amorphous material suitable for an optical semiconductor.

[0002]

2. Description of the Related Art Conventionally, as an amorphous optical semiconductor,
As described in "Basics of Amorphous Semiconductor" (published by Ohmsha), amorphous chalcogenide compounds such as selenium and tellurium have been widely used as photoelectric conversion members in image pickup tubes, light receiving elements, electrophotographic photosensitive members, and the like. In recent years, hydrogenated amorphous silicon has been used for solar cells, image sensors, and thin film transistors (Thin Film Tran).
used for electrophotographic photosensitive members.

However, amorphous chalcogenide compounds are unstable with respect to heat and are liable to be crystallized, so that the conditions under which they can be used are limited and valence electrons cannot be controlled.

On the other hand, hydrogenated amorphous silicon can control valence electrons, can realize a pn junction or an electric field effect at an interface, and has heat resistance up to about 250 ° C., but its photoconductivity is deteriorated by strong light. (Staebl
er, Wronski effect: Applied physics handbook) When used in a solar cell or the like, there is a problem that the efficiency is reduced during use due to deterioration due to light. Further, semiconductors including these elements are indirect transition types including crystals, and cannot be used for light-emitting elements, and their applications have been limited. As a material for solving the problems of these amorphous semiconductors,
Amorphous materials of III-V compound semiconductors have been studied.

Conventionally, an amorphous material of a group III-V compound semiconductor has been prepared by vapor deposition or sputtering of a group III-V crystal, or by using a group III metal as an atom and a molecule containing a group V element or an active molecule. Film formation by a reaction was performed. Further, an organic metal compound containing a group III metal and an organic metal compound containing a group V element are used to form a group III on a heated substrate.
-A group V film was produced (MOCVD method). When a crystal is formed on a substrate using these methods (600-100
By setting the substrate temperature to a lower temperature (0 ° C.), an amorphous group III-V compound is obtained. However, in this case, there was no amorphous III-V compound that could function as a photoelectric material due to problems such as carbon from the organic metal remaining in the film and many defect levels in the film.
[H. Reuter et al., Thin Solid Films, No. 254.
Vol. 94, 1995). On the other hand, it is known that amorphous hydrogen silicon is hydrogenated to reduce the density of defect states between bands and control valence electrons. Conventionally, a group III-V amorphous compound semiconductor has been hydrogenated by a reactive vapor deposition method or a reactive sputtering method. [Journal of Non-Crystal Solids (J. no
n-Cryst. Solids) Vol. 114, No. 73
2 (1989), 194, 103 (1
996), etc.] The introduction of hydrogen is expected to passivate dangling bonds caused by the group III atoms and group V atoms being bonded and becoming amorphous in the film. However, depending on the form of bonding to hydrogen atoms and the amount of hydrogen atoms introduced, there is a problem in that they react sensitively to air and easily cause oxidation reactions.

Further, in a III-V compound semiconductor,
It is known in the case of a crystal that the introduction of hydrogen may not only passivate dangling bonds but also inactivate a dopant for pn control at the same time. In particular, it is considered that the content of hydrogen and the bonding site in the film are problematic.

[0007]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned drawbacks of the amorphous III-V compound semiconductors, makes use of the role of hydrogen in the amorphous semiconductor, and has excellent photoconductive properties and high-speed response. An object of the present invention is to provide an amorphous material which has little change with time, has environmental resistance and high temperature resistance, is optically active, and is suitable as a new inexpensive optoelectronic material.

The present invention especially provides an amorphous nitride III-V compound semiconductor. Another object of the present invention is to provide a new optical semiconductor that can be manufactured safely, is low in cost, and has high performance.

[0009]

SUMMARY OF THE INVENTION The present invention provides an amorphous III-
The present invention has been completed by finding that the conventional disadvantages of group V nitride compound semiconductors can be improved by the bonding state between the element contained in the film and hydrogen.

That is, the amorphous material of the present invention comprises at least
Including hydrogen and group III elements and nitrogen in the periodic table
An infrared absorption spectrum of the amorphous material
Measured, the absorption peak that indicates the bond between nitrogen and hydrogen
Absorption peak indicating the bond between carbon (H), carbon and hydrogen
Ratio (I) of absorbance of absorption peak in (CH)_NH/ I
_CHIs 2 or more and the chip of the infrared absorption spectrum is
Absorption peak (N-H) indicating the bond between elemental and hydrogen and group III
The absorption peak (III-H) indicating the bond between the element and hydrogen
Ratio of the absorbance of the absorption peak in I_NH/ I_III-HIs 0.
It is characterized by being 2 or more.

Further, the group III element is gallium (Ga).
It is preferred that Here, the amorphous material of the present invention
When measuring the infrared absorption spectrum, the nitrogen and hydrogen
Absorption peak (N-H) indicating bond and bond between carbon and hydrogen
Of absorption peak at absorption peak (C-H) indicating
Degree ratio I_NH/ I_CHSpecifically, for example, III
If the group element is gallium (Ga), 32
30cm ^-1Near by the stretching vibration of NH in amorphous material
Absorption peak, 2950 cm^-1Stretching vibration of CH near
Absorption peak due to
Ratio I_NH/ I_CH(Ie, I₃₂₃₀/ I₂₉₅₀) Is 2 or more
In the infrared absorption spectrum,
Peaks (N-H) indicating the bond between nitrogen and group III elements
Absorption peak (III-H) indicating the bond between silicon and hydrogen.
Ratio of absorbance of absorption peak I_NH/ I_III-HIs 2
100cm^-1~ 2140cm^-1Ga-H stretching vibration
From the absorption peak due to the_NH/ I
_III-H(Ie, I₃₂₃₀/ I₂₁₀₀) Is 0.2 or more
Is shown.

The intensity of these absorption peaks also varies depending on the raw material of the amorphous material and the production method. Adjusting these intensity ratios within the above range means that the ratio of the group III element and nitrogen to hydrogen is suitably maintained, a good bonding state is exhibited, and the material constituting the amorphous material is included in the material. The amount of carbon present is small, more preferably, below the detection limit, the composition ratio of each element in the amorphous material is in a suitable state, and the obtained amorphous material shows stable and high performance Things.

Further, as a raw material of the group III element, III
It is preferable to use an organometallic compound containing a group III element, and it is preferable to use nitrogen gas or a hydride such as ammonia or hydrazone as a source of nitrogen.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail according to a manufacturing method.

An amorphous material suitable for the optical semiconductor of the present invention is:
It can be manufactured as follows. FIG. 1 is a conceptual diagram showing a semiconductor manufacturing apparatus suitable for manufacturing the amorphous material of the present invention. This semiconductor manufacturing apparatus is applied to a method using plasma as an activating means. Semiconductor manufacturing apparatus 10 of FIG.
A substrate holder 16 and a substrate heater 18 are arranged in a vacuum-evacuated container 14 having an exhaust port 12, and a quartz tube for introducing gas into the container 14 is provided in the container 14. (Hereinafter, appropriately referred to as a gas introduction pipe) 2
0 and 22 are connected.

[0016] For example as chip Motogen, using N ₂ gas and N ₂ gas _is introduced from gas introduction pipe 20 into the container 14. The gas introduction tube 20 is provided with a microwave waveguide 24 connected to a microwave oscillator using a magnetron, and a microwave of 2.45 GHz is supplied to the waveguide 24 so that the gas introduction tube (quartz tube) 20 is provided. Discharge is generated within
This discharge activates the N ₂ gas in the gas inlet tube 20.

For example, H ₂ is introduced into the other gas introduction pipe 22. The gas introduction tube 22 is provided with a high frequency coil 26 for supplying high frequency from a high frequency oscillator into the gas introduction tube 22. This high-frequency coil 26
A high frequency of 3.56 MHz is supplied to generate a discharge in the gas introduction tube (quartz tube) 22. Trimethyl gallium is introduced into the gas introduction tube 22 from a third gas introduction tube 28 provided on the downstream side of the discharge space. A material activated by microwaves or high frequencies in the respective gas introduction tubes 20 and 22 is introduced into the container 14, where amorphous gallium nitride is formed on the substrate.

FIG. 2 is a graph showing an example of an infrared absorption spectrum of a film formed using a Si wafer as a substrate. Here, gallium is used as the group III element,
Ga near 3230cm ^-1 according to the spectral absorption peak due to stretching vibration of N-H, in the vicinity of 2100 cm ^-1
There is an absorption peak due to stretching vibration of -H. Further 295
There is an absorption peak due to stretching vibration of C—H near 0 cm ⁻¹ . The intensity of these absorption peaks varies depending on the discharge power, the flow rate of the organometallic compound containing a Group III element, the flow rate and pressure of the compound containing a Group V element, and the type and amount of the raw material when using an auxiliary raw material. I do.

As the absorption intensity of the infrared absorption spectrum, the intensity corrected for the background was used, and the intensity ratio was 3230c.
The absorption intensities of the absorption peaks near m ^-1 and 2100 cm ^-1 can be represented as an infrared absorbance ratio. This is I ₃₂₃₀
/ I ₂₁₀₀ and means I _NH / I _{II IH} . Also, 3
I as the infrared absorbance ratio of 230cm ^-1 and 2950cm ^-1
₃₂₃₀ / I ₂₉₅₀ , which is I _NH / I _CH
Means When expressed as such, the value of I _NH / I _CH (specifically, I ₃₂₃₀ / I ₂₉₅₀ ) is 2 or more, and I _NH / I _CH is not less than 2.
/ I _III-H (specifically, I ₃₂₃₀ / I ₂₁₀₀ ) is 0.
Two or more films are in a stable state as an amorphous III-V nitride compound semiconductor (i.e., Ga-N semiconductor). Even if such a film is left in the air for a long period of time, the infrared absorption spectrum does not change, cracks and poor adhesion do not occur, the surface hardness is high, and the electrical and optical properties are excellent. Optical semiconductor material.

In the above example, an organometallic compound containing gallium as a group III element was used. In addition, an organometallic compound containing a group III element such as indium and aluminum can be mixed. Also in this case, a good amorphous material can be obtained by forming a film having an I _NH / I _III-H ratio of 0.2 or more. As described above, when a plurality of group III elements are used, the absorption peak (III-H) indicating the bond between the group III element and hydrogen is the absorption peak indicating the bond between each element and hydrogen (eg, Ga-H, In- H, Al-H
(Each peak in the combination).

The organometallic compound as a group III element raw material may be introduced from a gas introduction pipe 30 provided downstream of the microwave waveguide 24 instead of the gas introduction pipe 20. Further, by introducing a gas containing Si or Mg, an amorphous nitride of any conductivity type such as n-type or p-type can be obtained.
An IV semiconductor compound can be obtained.

The substrate temperature in this method is from 20 ° C. to 60 ° C.
It is preferably in the range of 0 ° C. By using a semiconductor manufacturing apparatus having at least two gas introduction pipes as described above, active nitrogen or active hydrogen can be controlled independently. As described above, even when a nitrogen material and a hydrogen material are not separately supplied, but a gas containing both nitrogen and hydrogen atoms such as NH ₃ is used, the active species of the group III and group V materials are not used. Preferred results can be obtained by independent control using such devices. That is, activated group III atoms and group V atoms are present in a controlled state on a substrate placed in a container, and activated hydrogen atoms form a methyl group, an ethyl group, or the like. In order to convert the film into molecules such as methane and ethane which are inactive to the film, carbon is hardly mixed in spite of the low temperature, and an amorphous film with reduced film defects can be produced.

Arranged as two activating means in the device are two different activating means, for example one may be a microwave oscillator, the other may be a co-high frequency oscillator, and both may be microwave oscillators. It may be a wave oscillator or a co-high frequency oscillator.

When a high-frequency discharge is used, it may be of an inductive type or a capacitive type. Further, an electron cyclotron resonance method may be used.

In the case of using different excitation means (activation means), it is necessary to enable discharge to occur simultaneously at the same pressure, and a pressure difference may be provided between the inside of the discharge and the film forming section.
In the case of using the same pressure, if different excitation means, for example, microwave and high-frequency discharge are used, the excitation energy of the excited species can be largely changed, which is effective for controlling the film quality.

Next, materials suitable for producing the amorphous material of the present invention will be described. The substrate used in the present invention may be conductive or insulating, and may be crystalline or amorphous.

As the conductive substrate, metals such as aluminum, stainless steel, nickel and chromium and alloy crystals thereof, for example, semiconductors such as Si, GaAs and SiC and crystals such as sapphire can be used.

Further, an insulating substrate having a substrate surface subjected to a conductive treatment may be used. As an insulating substrate,
Examples thereof include a polymer film, glass, and ceramic. These conductive treatments can be performed by forming a film of the metal, gold, silver, copper, or the like exemplified as the raw material of the conductive substrate by an evaporation method, a sputtering method, an ion plating method, or the like.

The transparent support of the transparent conductive substrate for inputting / outputting light may be a transparent inorganic material such as glass, quartz, sapphire, or a fluororesin, polyester, polycarbonate, polyethylene, polyethylene terephthalate, or the like. A transparent organic resin film or plate such as epoxy, an optical fiber, a SELFOC optical plate, or the like can also be used.

As the light-transmitting electrode provided on the light-transmitting support, a transparent conductive material such as ITO, zinc oxide, tin oxide, lead oxide, indium oxide, and copper iodide is used. And a metal such as Al, Ni, Au or the like formed by vapor deposition or sputtering so as not to impair the light transmittance.

Group III elements which are raw materials of an amorphous material suitable for the optical element member of the present invention include Al, Ga, and In.
It is preferable to be selected from the group consisting of

As the group III element raw material, besides the group III element itself, an organometallic compound containing one or more of these elements can be used. As the organometallic compound, for example, trimethylaluminum, triethylaluminum, tert-butylaluminum, trimethylgallium,
Liquids and solids such as triethylgallium, tert-butylgallium, trimethylindium, triethylindium and tert-butylindium can be used alone or in a mixed state by bubbling with a carrier gas.

As a carrier gas used for bubbling, a single element gas such as hydrogen or N ₂ gas, H 2
Noble gases such as e, Ar, Ne, etc., hydrocarbon gases such as methane and ethane, and halogenated carbons such as CF ₄ and C ₂ F ₆ can be used.

N ₂ , NH ₃ , N ₂
It can be used by vaporizing a nitrogen-containing gas or liquid such as F ₃ , N ₂ H ₄ or methylhydrazine, or bubbling with a carrier gas as described above.

In the amorphous material of the present invention, in addition to the above essential materials, for example, an element can be doped into the film for controlling p and n.

Examples of the n-type element include Li and I of the IA group.
Group B Cu, Ag, Au, Group IIA Mg, Group IIB Z
n, group IV Si, Ge, Sn, Pb, VIB group S, S
e and Te can be used. Among them, Si, Ge, S
n is preferred.

Examples of the p-type element include IA group Li, N
a, IB group Cu, Ag, Au, IIA group Be, Mg,
Ca, Sr, Ra, IIB group Zn, Cd, Hg, Ba,
IVB group C, Si, Ge, Sn, Pb, VIA group Cr,
Group VIB S, Se, Te, Group VIII Fe, Co, Ni and the like can be used. Above all, Be, Mg, Ca, Z
n and Sr are preferred.

As a method of doping these elements,
Is SiH for n-type_Four, Si_TwoH ₆, GeH_Four, Ge
F_Four, SnH_Four, And BeH for p-type_Two, BeCl_Two,
BeCl_Four, Cyclopentadienyl magnesium, dime
Chil calcium, dimethyl strontium, dimethyl sub
Lead, diethyl zinc, and the like can be used in the gaseous state. Also
It is diffused into the film as an element or taken into the film as ions.
It is also possible to apply known doping methods such as
it can.

Such an amorphous material containing at least one or more group III elements of Al, Ga, and In and nitrogen has a variable band gap in the entire region from red to ultraviolet, and has high light transmittance. The low dark conductivity and high light sensitivity make it possible to effectively use a wide range of light from the visible to the ultraviolet region. In addition, this amorphous material is excellent in light resistance, heat resistance, oxidation resistance and can respond at high speed, and also has a light emitting function that is not available in conventional amorphous semiconductors in all wavelength ranges,
It can also be used for a hybrid device combining an electronic device and a light emitting device. Specifically, high-efficiency solar cells,
High-speed TFT, high-sensitivity avalanche light sensor, large area L
Examples include an ED, a full-color display, an optical modulator, and an element for an optical interconnect. It can also be used as a growth buffer layer of a crystal layer, a charge injection blocking layer, an insulating layer, and the like.

[0040]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

Example 1 A substrate holder 16 in a container of a semiconductor manufacturing apparatus 10 as shown in FIG.
l Place the substrate, quartz substrate, Si wafer, and after evacuating, 2
Heated to 50 ° C.

N ₂ gas is introduced from the gas introduction pipe 20 to a diameter of 25 m.
m was introduced into a quartz tube of 500 m, and a microwave of 24.45 GHz was output by the microwave waveguide 24.
The battery was set at 0 W, and matching was performed with a tuner to perform discharge. The reflected wave at this time was 0W. 200 sccm of H ₂ gas was introduced from a gas introduction tube 22 into a quartz tube having a diameter of 30 mm, and discharge was performed at a high frequency of 13.56 MHz and an output of 100 W using a high frequency coil 26. The reflected wave was 0W. In this state, 1 sccm of trimethylgallium (TMGa) vapor kept at room temperature was introduced from the third gas introduction pipe 28 through a mass flow controller. At this time, the reaction pressure measured with a Baratron vacuum gauge was 0.2 Torr.
Met. Film formation was carried out under these conditions to obtain an amorphous material.
The composition of this film was measured by XPS, and the Ga / N ratio was 1.
A value of 1 was found to be approximately equivalent to stoichiometry. Optical Ga
p was 3.5 eV and it was colorless and transparent.

FIG. 3 shows the result of IR spectrum measurement of the amorphous material obtained in Example 1. The X-ray diffraction spectrum did not show a clear peak, indicating that it was amorphous. When the IR spectrum of this amorphous GaN film was measured after one week, one month, and two months, there was no change at all.

The peak around 3230 cm ^-1 and 2950c
The absorbance was determined by correcting the baseline for the peak near m ^-1 and the peak near 2100 cm ^-1 , and I ₃₂₃₀ /
I was asked to I _{29 50} and I ₃₂₃₀ / I _2100, respectively 17
And 0.28.

(Example 2) The same as Example 1 except that no high-frequency power was supplied without introducing H ₂ gas and that TMG was introduced from the gas introduction pipe 30 downstream of the microwave waveguide. A film of an amorphous material was formed using the apparatus.
N ₂ gas was introduced at 900 sccm, and microwave power was set to 200 W to perform discharge. TMG was introduced at 1 sccm.

As a result of measuring the IR spectrum of the amorphous material obtained in Example 2, no clear peak was observed in the X-ray diffraction spectrum, indicating that the material was amorphous. This amorphous G
When the IR spectrum of the aN film was measured after one week, one month, and two months, there was no change at all. In addition, no change was observed in the appearance of the amorphous GaN film even after the observation two months later.

The peak around 3230 cm ^-1 and 2950c
The absorbance was determined by correcting the baseline for the peak near m ^-1 and the peak near 2100 cm ^-1 , and I ₃₂₃₀ /
It was determined the I _{29 50} and I ₃₂₃₀ / I _2100, respectively 5.
4 and 0.22.

(Example 3) A microwave was set at an output of 250 W, H ₂ gas was introduced at 300 sccm, and TMGa was introduced.
Was introduced under the same conditions as in Example 1 except that 2 sccm was introduced to obtain an amorphous material.

As a result of measuring the IR spectrum of the amorphous material obtained in Example 3, the X-ray diffraction spectrum did not show a clear peak, indicating that it was amorphous. This amorphous G
When the IR spectrum of the aN film was measured after one week, one month, and two months, there was no change at all. In addition, no change was observed in the appearance of the amorphous GaN film even after the observation two months later.

The peak around 3230 cm ^-1 and 2950c
The absorbance was determined by correcting the baseline for the peak near m ^-1 and the peak near 2100 cm ^-1 , and I ₃₂₃₀ /
It was determined the I _{29 50} and I ₃₂₃₀ / I _2100, respectively 5.
6 and 0.24.

Example 4 A film was formed under the same conditions as in Example 1 except that the microwave was set to an output of 300 W and TMGa was introduced at 2 sccm to obtain an amorphous material.

As a result of measuring the IR spectrum of the amorphous material obtained in Example 4, the X-ray diffraction spectrum did not show a clear peak, indicating that the material was amorphous. This amorphous G
When the IR spectrum of the aN film was measured after one week, one month, and two months, there was no change at all. In addition, no change was observed in the appearance of the amorphous GaN film even after the observation two months later.

The peak around 3230 cm ^-1 and 2950c
The absorbance was determined by correcting the baseline for the peak near m ^-1 and the peak near 2100 cm ^-1 , and I ₃₂₃₀ /
It was determined the I _{29 50} and I ₃₂₃₀ / I _2100, respectively 9.
0 and 0.24.

(Comparative Example 1) An amorphous state was obtained by using the same apparatus as in Example 1 except that no H ₂ gas was introduced and no high-frequency power was supplied, and that TMG was introduced through the gas introduction pipe 30. A film of a porous material was formed. N ₂ gas is 300scc
m, and the microwave output was set to 150 W to perform discharge. TMG was introduced at 3 sccm. A film was formed under these conditions to obtain an amorphous material.

The color of the film after film formation was light brown.
FIG. 4 shows the IR spectrum of this amorphous material immediately after film formation. When the IR spectrum of this film was measured one week and two weeks later, the IR spectrum showed a large change. FIG. 5 shows the IR spectrum after two weeks. Ga-hydrogen and carbon-
The strength related to hydrogen bonding decreases, and G in the amorphous material
It can be seen that hydrogen bonded to a and carbon is reduced and oxidized. When the film was observed after two weeks, the color of the film became colorless and transparent, and generation of minute cracks was observed.
Peak Peak and 2950cm around ^-1 around 3230Cm ^-1 from the IR spectrum of the as deposited and 2100 cm ^-1
Was determined the I _{32 30} / I ₂₉₅₀ and I ₃₂₃₀ / I ₂₁₀₀ obtains the absorbance corrected baseline for the peak in the vicinity,
They were 0.8 and 0.1, respectively.

Comparative Example 2 A film was formed under the same conditions as in Comparative Example 1 except that N ₂ gas was introduced at 500 sccm to obtain an amorphous material.

The color of the formed film was light brown.
The IR spectrum of this amorphous material immediately after film formation was measured,
Further, when the IR spectrum was measured one week and two weeks later, the IR spectrum showed a large change as in Comparative Example 1. After 2 weeks, the color of the film became colorless and transparent, and generation of minute cracks was observed. From the IR spectrum immediately after the film formation, a peak around 3230 cm ^-1 and 29
50cm for near peak and 2100 cm ^-1 peaks near ^-1 obtains the absorbance corrected baseline I ₃₂₃₀
/ I ₂₉₅₀ and I ₃₂₃₀ / I ₂₁₀₀ were 1.9 and 0.09, respectively.

(Comparative Example 3) N ₂ gas was introduced at 500 sccm, H ₂ gas was introduced at 200 sccm, no high-frequency power was supplied, and TMG was introduced at 3 sccm.
A film was formed under the same conditions as in Comparative Example 1 except that the gas was introduced from the gas introduction pipe 30 to obtain an amorphous material.

The color of the film after film formation was light brown.
The IR spectrum of this amorphous material immediately after film formation was measured,
Further, when the IR spectrum was measured one week and two weeks later, a slight change was observed in the IR spectrum. Further, after a week, the color of the film became colorless and transparent, the adhesion between the film and the base material was reduced, and a peeled portion was observed. Seeking I ₃₂₃₀ / I ₂₉₅₀ and I ₃₂₃₀ / I ₂₁₀₀ obtains the absorbance corrected baseline for the peak of the peak and 2100cm around ^-1 peak and 2950cm around ^-1 around 3230Cm ^-1 from the IR spectrum immediately after the film formation As a result, they were 1.5 and 0.11, respectively.

The amorphous materials I ₃₂₃₀ / I ₂₉₅₀ ,
₃₂₃₀ / I ₂₁₀₀ and time course of nature and IR spectrum of the film, the contrast conductivity ratio for photoconductivity by Xenon lamp irradiation, as shown in Table 1 below.

[0061]

[Table 1]

As is evident in Table 1, the ratio of the absorbances I _NH /
The amorphous materials of Examples 1 to 4 in which I _CH and I _NH / I _III-H are within the scope of the present invention all form uniform and transparent films, and are excellent in photoconductivity. Further, there was almost no change over time, and the environment resistance was excellent. On the other hand, the amorphous materials of Comparative Examples 1 to 3 in which the absorbance ratios I _NH / I _CH and I _NH / I _III-H are within the range of the present invention have insufficient photoconductivity, The color changed over time in a short period of up to 2 weeks, furthermore, generation of minute cracks and decrease in adhesion to the substrate were observed, and the stability was poor.

The conditions for obtaining a suitable amorphous material according to the present invention can be selected according to various correlations such as raw materials and conditions. From the results of the above-mentioned Examples and Comparative Examples, the amount of N ₂ gas introduced can be reduced. It can be seen that preferable examples include a large amount, a high microwave energy applied to the N ₂ gas, a small introduction amount of the group III element, a supply of the H ₂ gas, and activation by a high frequency.

[0064]

As described above, the amorphous material of the present invention is made of a conventional amorphous II
It has improved the disadvantages of group IV compound semiconductors, has excellent photoconductive properties and high-speed response, and is stable over time, and has excellent effects of having environmental resistance and high temperature resistance.

[Brief description of the drawings]

FIG. 1 is a schematic view showing a semiconductor manufacturing apparatus that can be suitably used for manufacturing an amorphous material of the present invention.

FIG. 2 is a graph showing a model IR spectrum of the amorphous material of the present invention.

FIG. 3 is a graph showing an IR spectrum immediately after film formation of an amorphous material of Example 1.

FIG. 4 is a graph showing an IR spectrum immediately after film formation of an amorphous material of Comparative Example 1.

FIG. 5 shows I after two weeks of film formation of the amorphous material of Comparative Example 1.
It is a graph which shows an R spectrum.

DESCRIPTION OF SYMBOLS 10 Semiconductor manufacturing apparatus 12 Exhaust port 14 Container that can be evacuated to vacuum 16 Substrate holder 18 Substrate heater 20 Quartz tube for introducing gas (gas introduction tube) 22 Quartz tube for introducing gas Gas introduction tube) 24 Microwave waveguide 26 High frequency coil 28 Third gas introduction tube 30 Gas introduction tube downstream of microwave waveguide

Claims (4)

[Claims] 1. At least hydrogen and II in the periodic table
An amorphous material containing a Group I element and nitrogen. When an infrared absorption spectrum of the amorphous material is measured, an absorption peak (N—H) indicating a bond between nitrogen and hydrogen and carbon are measured. The ratio of the absorbance I _NH / I _CH of the absorption peak at the absorption peak ( _CH ) showing the bond with hydrogen is 2 or more;
In addition, the ratio of the absorbance I between the absorption peak (N-H) indicating the bond between nitrogen and hydrogen and the absorption peak (III-H) indicating the bond between the Group III element and hydrogen in the infrared absorption spectrum
_An amorphous material having an _NH / I _{II IH} of 0.2 or more. 2. The group III element is gallium (Ga), and the ratio I ₃₂₃₀ / I ₂₉₅₀ of the absorption peak of the amorphous material near ₃₂₃₀ cm ⁻¹ and 2950 cm ^{−1 in} the infrared absorption spectrum is 2 2. The ratio I ₃₂₃₀ / I ₂₁₀₀ of absorption peaks at around ₃₂₃₀ cm ^{−1 and} around ₂₁₀₀ cm ⁻¹ in the infrared absorption spectrum is 0.2 or more. Amorphous material. 3. The amorphous material according to claim 1, wherein an organic metal compound containing a Group III element is used as a raw material of the Group III element. 4. The amorphous material according to claim 1, wherein nitrogen gas is used as a nitrogen source.