JPS62193242A - Formation of deposit film - Google Patents

Abstract

PURPOSE:To contrive the homogeneity of film quality by forming a valence- electron-controlled deposit film on a substrate which is heated and held in a film-forming space by using a precursor for the supply source of the elements constituting the deposit film. CONSTITUTION:At least either one of a formed excited state precursor and other precursors is used for the supply source of the elements constituting a formed deposit film. The formed precursor is made another excited state precursor by decomposition or reaction or emits energy but is brought into contact with the surface of a substrate which is heated and held in a film-forming space in its original state, heat energy, etc., are supplied from the substrate and an epitaxial deposit film is formed. The process of forming the epitaxial deposit film is carried out efficiently since the previously activated precursor exists. This enables obtaining an epitaxial deposit film which is homogeneous and has excellent characteristics on all the surface of the film.

Description

Detailed Description of the Invention [Technical Field to which the Invention Pertains] The present invention relates to functional gonads, especially semiconductor devices, optical input sensor devices for optical image input devices, and uses of electronic devices such as photosensitive devices for electrophotography. The present invention relates to a method for forming a semiconductor epitaxially deposited film useful for.

[Description of conventional technology]

Conventionally, functional gonads, particularly crystalline semiconductor films, have been formed using various film formation methods from the viewpoint of desired physical properties, applications, and the like.

For example, to form an epitaxially deposited film of silicon,
Broadly speaking, gas phase epitaxy and liquid phase epitaxy are used.

Liquid phase epitaxy is a method in which a raw material for a semiconductor is dissolved in a liquid metal bath medium at high temperature to a supersaturated state, and the solution is cooled to deposit semiconductor crystals on a substrate.

According to this method, crystals are created in a state that is closest to the thermal plane among the Evitagishi technologies in each building, so crystals with high perfection can be obtained, but on the other hand, it is difficult to mass produce and the surface condition is poor.
In optical devices that require a thin and uniformly thick epitaxial N layer, it is not used very often because of problems such as slow manufacturing steps and adverse effects on device characteristics.

On the other hand, vapor phase epitaxy has been attempted using physical methods such as vacuum evaporation and sputtering, or chemical methods such as hydrogen reduction of metal chlorides and thermal decomposition of organic metals or metal hydrides. Among them, molecular beam epitaxy, which is a type of vacuum evaporation method, is a dry process under ultra-high vacuum, so it is possible to achieve high purity crystals and grow them at low temperatures.
P1! This has the advantage of good controllability and the ability to obtain a relatively flat deposited film, but in addition to the enormous cost of the film-forming equipment, the optical surface defect density is high, and the orientation of the molecular taste is high. It has not yet been commercialized because an effective method for controlling sex has not yet been developed, and there are many problems such as difficulty in increasing the area and poor mass production.

The hydrogen reduction method of metal chlorides or the thermal decomposition method of enriched metals or metal hydrides are called halide CV[)i, hydride CVD method, MO-CVD method, and these methods are used for film formation. As equipment can be manufactured relatively easily, and highly pure metal chlorides, metal hydrides, and organic metals used as raw materials can be easily obtained, it is now widely used to grind various types of maple. Applications to devices are also being considered.

However, in these methods, it is necessary to heat the substrate to a high enough temperature to cause a reduction reaction or a thermal decomposition reaction, which limits the range of substrate material selection, and may result in insufficient decomposition of the raw materials. If so, contamination with impurities such as carbon or halogen is likely to occur, and doping controllability is poor. Furthermore, depending on the application of the deposited film, there is a desire to achieve mass production with high reproducibility through high-speed film formation while satisfying the requirements of large area, uniform thickness, and uniform film quality. The reality is that no technology has yet been established that enables FT production while maintaining practical properties that satisfy the requirements for storage.

In this way, we are currently developing a method for forming epitaxially deposited films of silicon or germanium with controlled valence electrons, which can be produced in reduced quantities using low-cost equipment while maintaining its practical characteristics and uniformity. There is a strong need for development.

[Purpose of the invention]

The main object of the present invention is to eliminate the above-mentioned drawbacks of vapor phase epitaxy and to provide a novel epitaxially deposited film formation method that does not rely on conventional formation methods.

Another object of the present invention is to improve the properties, film formation speed, and reproducibility of the epitaxial film to be formed, and to make the film uniform in quality, while also being suitable for large-area films, improving film productivity, and The object of the present invention is to provide a method for forming an epitaxially deposited film that can be easily mass-produced while saving energy.

[Structure of the invention]

The present invention was completed as a result of intensive research by the present inventors in order to overcome the above-mentioned problems and achieve the object of the present invention, and includes a gaseous raw material for forming a deposited film, A gaseous halogen-based oxidizing agent having the property of oxidizing the raw material and a gaseous substance containing a component serving as a valence electron control agent are introduced into a reaction space and brought into contact with each other to form an excited state. producing a plurality of precursors, including at least one of the precursors, and depositing at least one of the precursors onto a heated and maintained substrate within the deposition space as a source of deposited film components. This is a deposited film forming method characterized by forming a deposited film.

According to the deposited film forming method of the present invention having the above-mentioned configuration, it is possible to save energy, reduce energy consumption, and improve film thickness uniformity.

By fully satisfying the uniformity of film quality and simplifying management and mass production, there is no need for large capital investments in mass production equipment, and the management items for the 7 Ti have been clarified, allowing for a wider range of control. It is wide, and it is easy to adjust the distortion of the device.

In the method for forming a deposited film of the present invention, a gaseous raw material for forming a deposited film (hereinafter referred to as "gaseous raw material (I)") is used.
It is called. ) and a component that becomes a valence control agent (hereinafter referred to as "substance (■)") is a gaseous halogen-based absorbing agent (hereinafter referred to as ")" and a halogen-based oxidizing agent ( ■)" ), and the oxidizing effect can be increased by contact with ), and is appropriately selected depending on the type, characteristics, application, etc. of the desired deposited film. In the method of the present invention, the above gaseous raw material (1), the gaseous substance (I
II) and the gaseous halogen thread oxidizing agent (I[) may be anything that is in a gaseous state when introduced and brought into contact.
In normal cases, it may be gas, liquid, or solid.

Gaseous raw material for forming deposited film'] (I), thing! <1
it) or Ar, He when the halogen-based oxidizing agent (■) is liquid or solid under normal conditions.

Using a carrier gas such as N, H2, etc., and performing bubbling while heating if necessary, the gaseous raw material (1), substance (ill), and halogen-based oxidizing agent for forming a deposited film are placed in the reaction space. (If) is introduced in gaseous form.

Except for this, the above gaseous raw material vlJ quality (1), gaseous substance (
The partial pressure and mixing ratio of the gaseous halogenated oxidizing agent (it) and the gaseous halogenated oxidizing agent (it) are determined by the flow rate of the carrier gas or the vapor of the gaseous raw material (I) and the gaseous halogenated oxidizing agent (II) for forming the deposited film. It is set by adjusting the pressure. Furthermore, when the gaseous raw material (1), the substance (ill), or the halogen-based oxidizing agent (11) is a gas in the normal state, Ar, He, N,
It can also be diluted and introduced with a carrier gas such as , H, or the like.

The gaseous raw material (1) for forming a deposited film used in the method of the present invention may include linear or branched chains if a silicon epitaxial deposited film and a germanium epitaxial deposited film are to be obtained. Effective examples include silane compounds, cyclic silane compounds, and chain germanium compounds.

Specifically, the linear silane compounds include Si, H2n
+z (n = 1.2.3.4.5.6.7.8), branched chain silane compounds include SiH, 5iH (Si
H,) SiH,5i)i3, as a cyclic silane compound, 5in1(2n (n = 3.4.5.6),
As a chain germane compound, QemHzm+z (m
= 1.2°3, 4.5), etc.

Of course, these silicon-based compounds or germanium-based compounds can be used in a mixture of not only 12m but also 28 or more.

The halogen-based oxidizing agent (I) used in the method of the present invention
[) is in a gaseous state when introduced into the reaction space, and has the property of effectively oxidizing just by contacting the gaseous raw material (I) for forming a deposited film, which is simultaneously introduced into the reaction space. with F,, C12,Br,, It,
Halogen gas such as CIF can be cited as an effective gas.

These halogen-based oxidizing agents (II) are in gaseous form, and together with the above-mentioned raw material 'J ((I) gas and the above-mentioned substance (III) gas), a desired flow rate and supply pressure are applied. is introduced into the reaction space and causes a chemical reaction by mixing and colliding with the raw material substance (1) and the substance (1),
The source material (1) and the substance (1) are oxidized to efficiently produce several precursors including excited state precursors.

The excited state precursors and other precursors that are generated serve as a source of components for the deposited film in which at least one of them is formed.

The generated precursor decomposes or reacts to become a precursor in another excited state or a precursor in another excited state, or it releases energy as necessary but forms a film as it is. An epitaxially deposited film is created by touching the surface of a heated substrate disposed in a space and being supplied with thermal energy or the like from the substrate.

The epitaxially deposited film formation process of the present invention is more efficient due to the presence of pre-activated precursors;
An epitaxially deposited film that proceeds with less energy, is uniform over the entire surface of the film, and has better physical properties is formed at a lower substrate temperature than conventionally.

In the method of the present invention, a substance containing a component that becomes a valence electron control agent! As (ill), it is preferable to select a compound that is in a gaseous state at normal temperature and normal pressure, or at least under the conditions for forming a deposited film, and that can be easily vaporized using an appropriate vaporizing device.

As the substance (III) used in the method of the present invention, when forming a silicon epitaxial film and a germanium epitaxial film, a pm valence electron control agent,
Elements of group Ⅰ A of the periodic table that act as p-type impurities, such as B, AJ, and Ga.

A compound containing In, T1, etc., and an n-type valence electron control agent,
Examples include compounds containing elements of Group ⅠA of the periodic table, such as N, P, As, Sb, and Bi, which act as n-type impurities.

Specifically, NH3, HN, , N,)1. N, ,
N! H4°NH, N8. PH3, P! H,,AsH
3,8bH8,BiH,.

BtH6,B,H,. ,”'!H,,BS)its
-86)il. , B, H,.

kl (CH3)3, A7 (C,Hs)s,
Effective examples include Ga(CHs)a and In(CHs)a.

the above? ! [In order to introduce the gas into the gaseous reaction space of (Ill), it can be mixed with the gaseous raw material (1) for forming the deposited film beforehand, or it can be introduced from a plurality of independent gas supply sources. be able to.

In the method of the present invention, the process of forming a deposited film proceeds smoothly, and a film having high quality and desired physical properties can be formed, and the gaseous raw material for forming the deposited film is used as a film-forming factor. (I), substance (1), and halogen-based oxidizing agent (II), their mixing ratio, the pressure during mixing, the flow rate, the internal pressure of the film-forming space, the gas flow type, the film-forming temperature (substrate temperature and ambient temperature) are appropriately selected as desired.

These film-forming factors are organically related and are not determined independently, but are determined depending on each other in relation to each other.

In the method of the present invention, $1fR introduced into the reaction space
The ratio of the amounts of the gaseous raw material (I) for film formation and the gaseous halogen-based oxidizing agent (ml) is appropriately determined as desired in relation to the relevant film-forming factors among the above-mentioned film-forming factors. is the introduction #f, m ratio, preferably 1/20 to 1
00/1 is appropriate, more preferably 115-50/
It is desirable to set it to 1.

Further, the ratio of introduction of the gaseous substance 'J[(lit) may be set as desired depending on the type of the gaseous raw material (1) and the desired semiconductor characteristics of the deposited film to be created. , preferably 1/1000000 to 1/10, more preferably 1
/ 100000 to 1/20, optimally 1/100
It is desirable to set it to 000-1150.

The pressure at the time of mixing when introduced into the reaction space is set to increase the probability of contact between the gaseous raw material (1) and the gaseous substance 'X(I[) and the gaseous halogen-based oxidant (former) For this purpose, it is better to have a higher value, but it is better to determine the optimum value as desired by considering the reactivity.The pressure during the mixing can be determined as described above, but the pressure for each The pressure at the time of introduction is preferably i x 10' atmosphere ~
It is desirable that the pressure be 5 atm, more preferably 1X10' to 2 atm.

The pressure in the deposition space, that is, the pressure in the space where the film is to be deposited on its surface, is due to the excited state precursor generated in the reaction space and, if necessary, from the precursor. The pre-conductor 114 is set as desired so as to effectively contribute to the film forming process.

If the film forming space is open and continuous with the reaction walls, the pressure in the film forming space is the gaseous raw material for forming the deposited film! vJ/
In relation to the equation and flow rate in the reaction space of x (■), the substance (Ill), and the gaseous halogen-based oxidizer (it), for example, use of differential co-airing or a large exhaust system. It is possible to make adjustments by adding such measures.

Alternatively, if the conductance of the connection between the reaction space and the film-forming space is small, an appropriate exhaust system may be provided in the film-forming space.
The pressure in the film forming space can be adjusted by controlling the evacuation of the device.

Furthermore, if the reaction space and film-forming space are integrated and the reaction position and film-forming position differ only in total volume, differential pumping as described above or pumping capacity light A large exhaust system should be installed.

As described above, the pressure in the film forming space is determined by the relationship between the gaseous raw material w negative (1) introduced into the reaction space, the gaseous substance (ill), and the introduction pressure of the gaseous halogen oxidant (II). However, preferably 0.0 (11 To
rr ~ 100 Torr, more preferably 0
, (11 Torr ~ 3Q Torr, optimally,
It is desirable to set it to 0.05 Torr - 10 Torr.

Regarding the flow rate of the gas, the raw material material (1) for forming the deposited film, the material (1), and the halogen-based oxidizing agent (
When introducing Il), these are mixed uniformly and efficiently,
In order to efficiently generate the precursor and to properly form a film without any trouble, it is necessary to take into consideration the geometrical arrangement of the gas inlet, the substrate, and the gas outlet. One preferred example of this geometry is shown in FIG. 1, which will be discussed in more detail below.

In the method of the present invention, in order to form a high quality epitaxial film, it is preferable to use a single crystal substrate such as Si or GaAs. ) crow or a
A non-single crystal substrate such as -8i (amorphous silicon) or an insulating substrate such as sapphire crystal can be used, and an epitaxial film can also be formed on the substrate.

The substrate temperature (Ts) during film formation is appropriately set depending on the S type of the deposited film to be formed and the type of substrate used, but is preferably 3.
00C~100OC, more preferably 400C~900
It is preferable to use C, and if a substrate with good orientation is used, a high quality epitaxial film can be formed at a low substrate temperature. When forming an epitaxial film of kermanium, the temperature is preferably 250C to 5ooc, more preferably 350C to 700C, and if a substrate with good orientation is used, a high quality epitaxial film can be formed at a low substrate temperature. It becomes possible to form

〔Example〕

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited by these Examples.

FIG. 1 shows an example of an apparatus suitable for implementing the present invention for forming a deposited film.

The deposition/film forming apparatus shown in FIG. 1 is roughly divided into three parts: an apparatus main body, an exhaust system, and a gas supply system.

The apparatus main body is provided with a reaction space and a film forming space.

1 (11 to 108 are cylinders filled with gas used for film formation, respectively; 1 (11a to 108a are gas supply pipes, respectively; 1 (11b to 108b are gas flow rate adjustment from each cylinder) mass flow controller for
1 (11C to 108C are gas field power meters, 1 (11
d to 108d and 1(11e to 108e are pulps, respectively, and 1(11f to 108f are pressure gauges indicating the pressure in the corresponding gas cylinders, respectively.

Reference numeral 120 denotes a vacuum chamber, which has a structure in which a piping for introducing gas is provided at the upper part and a reaction space is formed downstream of the piping.
It has a structure in which a film forming space is formed in which a substrate holder 112 is provided such that a substrate holder 18 is installed therein. The piping for gas introduction has a three-meter concentric configuration, and the gas cylinder 1 (11.
, a second gas introduction pipe 110 into which gases from gas cylinders 1 (13 to 105 are introduced), and a third gas introduction pipe 111 into which gases from gas cylinders 106 to 108 are introduced.

Gas is supplied from the cylinder to each introduction pipe through gas supply pipelines 123 to 125, respectively.

Each gas introduction pipe, each gas supply pipeline, and the vacuum chamber 120 are evacuated by a vacuum evacuation device (not shown) via the main vacuum pulp 119.

The substrate 118 is placed at a desired distance from the position of each gas introduction pipe by moving the substrate holder 112 up and down.

In the case of the method of the present invention, the distance between the substrate and the gas inlet of the waste inlet tube is determined appropriately by considering the consistency of the deposited film to be formed, its desired characteristics, gas flow rate, internal pressure of the vacuum chamber, etc. Although it is determined according to the condition, preferably several meters
m −20 cm.

More preferably, it is desirable to set it as 5 mm - 15 cmg degrees.

113 is a substrate heating device that heats the substrate 118 to an appropriate temperature during film formation, or preheats the base 118 before film formation, or further heats the substrate 118 to 7 anneal the film during film formation. It's a heater.

The heater 113 for heating the substrate is connected to the power supply 1 via a conductor 114.
Power is supplied by 15.

116 is a thermocouple for measuring the substrate temperature (Ts), and is electrically connected to the temperature display device 117.

Example 1 Using the film forming apparatus shown in FIG. 1, a deposited film was produced by the method of the present invention in the following manner.

Cylinder 1 (11 K light-treated SiH, gas was introduced from V109 at a flow rate of 30 sec, and cylinder 1 (13
Race to be filled with light: Ile B, F-16A (5000
ppm He gas dilution) m: 1ltO05sccm,
At 5 sccm and 50 sccm, the F and waste filled in the cylinder 106 are passed through the gas introduction pipe 110 by a current of 40 sccm.
Sccm, Le gas (filled in the cylinder 107) was introduced into the vacuum chamber 120 from the gas passageway 111 at a flow rate IQQSCCm.

At this time, the pressure inside the vacuum chamber 120 is increased to 1ill! the degree of opening and closing of the vacuum pulp 119 is increased! The pressure was set to 0.5 Torr. An n medium size Si single crystal wafer having a diameter of 3 inches was used as the substrate 118, and the distance between the gas inlet 111 and the substrate was set at 15 cmK. 8iH, strong bluish-white light emission was observed in the mixed region of gas, F, and gas. The substrate temperature (Ts) was set at 8,000.

When gas was allowed to flow in this state for 1 hour, a 15 μm silicon epitaxial deposited film was formed on the substrate.

When the crystallinity of the obtained silicon epitaxially deposited film sample was examined by X-ray diffraction, it was found that growth occurred in the (100) plane, which is the same as the crystal plane of the 8i single crystal wafer substrate used, and that there were few lattice defects. It was confirmed.

Further, when the surface condition was observed using a scanning electron microscope, the smoothness was good and there was no wave pattern, etc., and the film thickness unevenness was ±5% or less.

The doping characteristics of each sample at room temperature were determined by van derPa
When evaluated by the uw method, the results shown in Table 1 were obtained. It was found that better pm doping was achieved than this.

Table 1 Example 2 In Example 1, a p+ type S1 single crystal substrate was used instead of the n+ type Si single crystal wafer substrate, and further B, )16
Instead of gas, use cylinder 1 (PH filled in 14,
Gas (6000 ppm He gas dilution) flow rate, 0,
5 sccm, 5 sccm, 50 sccm
A deposited film was formed under the same film forming conditions except that the gas was introduced from the gas introduction pipe 110 at 100 m, and the doping characteristics of the obtained epitaxial film at room temperature were evaluated by van der pauw, and the results shown in Table 2 were obtained. Ta.

From this, it was found that good n-type doping was performed.

Table 2 Example 3 Deposition was performed under the same film forming conditions as in Example 1, except that 10αXl0cIn quartz glass was used instead of the n-medium 8i single crystal wafer substrate, the F2 gas flow rate was 50 sec, and the substrate temperature was 850C. A film was formed.

The crystallinity of the obtained silicon epitaxially deposited film sample was evaluated by X#81 diffraction method.
It was confirmed that the growth of the 00) plane occurred on a surface that was flat with the substrate, and that there were few lattice defects.

In addition, when the surface condition and plate were observed using a scanner, the smoothness was good with no wave patterns, and the film thickness was uneven by ±5%.
It was below.

Doping characteristics of each sample obtained at room temperature
When evaluated by the Er Pauw method, the results shown in Table 3 were obtained. From this, it was found that good p-type doping was performed.

Table 3 Example 4 In Example 3, the SiH gas flow rate was 40 sec, and instead of B, H, and gases (5000 ppm He gas dilution), Pf (3 gases (6000 ppm He gas dilution) was added at 0.5 sec, 5 sccm,
An epitaxially deposited film was formed under the same film forming conditions except that the deposition rate was 45 sccm.

The doping characteristics of each sample obtained at room temperature were
When evaluated by the Er Pauw method, the results shown in Table 4 were obtained. From this, it was found that good n-type doping was performed.

Table 4 Example 5 In Example 1, a sapphire base crystal substrate was used instead of the n medium size Si single crystal wafer substrate, SiH, gas flow rate was 20 sec F, and gas flow rate was 15 sec.
A deposited film was formed under the same film forming conditions except that the substrate temperature was 850C.

The crystallinity of the obtained silicon epitaxially deposited film sample was evaluated by X-ray diffraction method.
) plane growth occurred on the surface parallel to the substrate, and it was confirmed that lattice defects were also small.

Further, when the surface condition was observed using a scanning Hiroko microscope, it was found that the smoothness was good, there was no wave pattern, etc., and the film thickness unevenness was less than ±5%.

The doping characteristics of each sample obtained at room temperature were
When evaluated by the Er Pauw method, the results shown in Table 5 were obtained. From this, it was found that good p-type doping was performed.

Table 5 Example 6 In Example 5, the SiH4 gas flow rate was 39 sec, B, 86 is (5000 ppm He gas dilution)
K, PH, gas (6000 ppm He gas dilution) at 0.5 sccm, 5 sccm, 45
An epitaxially deposited film was formed under the same film forming conditions except that the doping characteristics of each of the obtained samples at room temperature were evaluated by the van der Pauw method, and the results shown in Table 6 were obtained. From this, it was found that good n-type doping was performed.

Table 6 Example 7 In this example, GeH4 gas filled in cylinder 1 (12) was introduced into gas inlet pipe 110 at a flow rate of 20 sec.
From 9, flow the B, H, gas (5000 ppm He gas diluted) filled in cylinder 1 (13).
ccm, 4sccm, 4Q sccm from the gas introduction pipe 110, the F gas filled in the cylinder 106 has a flow rate of 30 seconds, and the He gas filled in the cylinder 107 has a flow rate of 9Q sccm and passes through the gas introduction pipe 111.
was introduced into the vacuum chamber 120.

At this time, the pressure inside the vacuum chamber 120 was adjusted to 0.4 Torr by adjusting the degree of opening and closing of the vacuum pulp 119. An n0-type GaAs single crystal wafer having a diameter of 2 inches was used as the substrate 118, and the distance between the gas inlet 111 and the substrate was set to 5 cm. Strong blue-white light emission was observed in the mixed region of GeH, gas, and F2 residue. The substrate temperature (Ts) was set at 550C.

When gas was allowed to flow in this state for 1 hour, a 10 μm epitaxial deposited film of germanium was formed on the substrate.

When the crystallinity of the obtained germanium epitaxially deposited arm sample was evaluated by X-ray diffraction, it was found that the Ga used
It was confirmed that growth occurred in the (100) plane, which is the same as the crystal plane of the As single crystal substrate, and that there were few lattice defects.

Further, when the surface condition was observed using a scanning Hiroko microscope, it was found that the smoothness was good and there was no wave pattern, and the film thickness unevenness was less than ±5%.

The doping characteristics of each sample at room temperature were determined by van derPa
When evaluated by the uw method, the results shown in Table 7 were obtained. It was found that better doping of paM was achieved than this.

Table 7 Example 8 In Example 7, a p raw temperature Ga A3 single crystal substrate was used instead of the n raw type QaAs single crystal wafer substrate, and further B2)1. Instead of gas, use the PH gas (6000 ppm f4e gas distribution) filled in cylinder 1 (14) at a flow rate of 0.5 sccm, 45 can, 4
A deposited layer was formed under the same film forming conditions except that the gas was introduced from the gas introduction pipe 110 at 5 sccm, and the doping characteristics of the obtained epitaxial film at room temperature were determined by van der Pau.
When evaluated by the W method, the results shown in Table 8 were obtained. From this, it was found that good n-type doping was performed.

Table 8 Example 9 In Example 7, a 10 cm x 10 cm quartz glass was used instead of the W GaAs single crystal wafer substrate, the F gas flow rate was 40 sccm, and the substrate temperature was 60 sccm.
A deposited film was formed under the same film forming conditions except that the temperature was 0C.

The crystallinity of the obtained germanium epitaxia/L/deposited film sample was evaluated by Xi diffraction method, and it was found that the growth of the germanium (100) plane occurred on the surface parallel to the substrate, and there were few lattice defects. confirmed.

Further, when the surface condition was observed using a scanning electron microscope, the smoothness was good, there was no wave pattern, etc., and the film thickness unevenness was less than ±5%.

The doping characteristics of each sample obtained at room temperature were
When evaluated by the Er Pauw method, the results shown in Table 9 were obtained. From this, it was found that excellent p-type doping was performed.

Table 9 Example 10 In Example 9, the GeH4 gas flow rate was 25 sec, and B, H6 gas (5000 ppm He scum dilution)
t)') Instead, PH, gas (6000ppm H
e gas dilution) at 0.5 sccm, 4 sccm,
An epitaxially deposited film was formed under the same film forming conditions except that the deposition rate was 35 sccm.

The doping characteristics of each sample obtained at room temperature were
When evaluated by the Er Pauw method, the results shown in Table 10 were obtained. From this, it was found that good n-type doping was performed.

Table 10 Example 11 In Example 7, a sapphire single crystal substrate was used instead of the n medium-sized GaAs single crystal Unino 1 substrate, and (jeH,
Gas flow rate is 3Q sccm, F2 gas flow rate is 5Q
The deposited film was formed under the same film forming conditions except that the temperature was set to sccm and the substrate temperature was set to 580C.

When the crystallinity of the obtained germanium epitaxially deposited film sample was evaluated by Xls diffraction method, it was confirmed that the growth of the (100') plane of germanium occurred on the surface parallel to the substrate and that there were few lattice defects.

Further, when the surface condition was observed using a scanning Hiroko microscope, it was found that the smoothness was good and there was no wave pattern, etc., and the film thickness unevenness was less than ±5%.

The doping characteristics of each sample obtained at room temperature were
When evaluated by the Er Pauw method, the results shown in Table 11 were obtained. From this, it was found that good p-type doping was performed.

Table 11 Example 12 In Example 11, the GeH4 gas flow rate was set to 358 CCm, and instead of B, H, gas (5000 ppm He gas dilution), PH, gas (6000 ppm He gas dilution) was used at 0.5 sccm, 5 sccm, 45
An epitaxially deposited film was formed under the same film forming conditions except that sccm was used.

The doping characteristics of each sample obtained at room temperature were
When evaluated by the Er Pauw method, the results shown in Table 12 were obtained. From this, it was found that good n-type doping was performed.

Table 12 [Effects of the Invention] The deposited film forming method of the present invention can generate an excited state precursor simply by bringing the gaseous raw material and the gaseous halogen-based edifying agent into contact with each other. It has the advantage that the excitation energy is not particularly required, and therefore it is possible to lower the temperature of the substrate chromatism.

Moreover, it is possible to obtain an epitaxially deposited film having uniform film quality and characteristics over a large area, which is effective in energy saving, and at the same time, allows easy control of film quality. Furthermore, it is possible to easily obtain epitaxially deposited films with excellent productivity and mass production, and with high quality and excellent physical properties such as electrical, optical, and semiconductor properties.

[Brief explanation of drawings]

Figure @1 is a schematic diagram of a film forming apparatus used in an example of the present invention. In the figure, 1 (11 to 108-... gas conduction/be, 1 (11a to 10
8a...Gas introduction pipe, 1 (11b-108b...
・Mass 70 meters, 1 (11C ~ 108C... Gas pressure gauge, 1 (11d ~ 108d and 1 (11e ~ 1
088--Pulp, 1 (11f-108f...Pressure gauge, 109, 110, 111, 123-125
... Gas introduction pipe, 112 ... Substrate holder, 113
... Heater for heating the substrate, 114 ... Conductive wire, 115
...Power supply, 116...Thermocouple for board temperature monitoring,
117...Temperature display device, 118...Substrate, 119
...Vacuum evacuation pulp, 120°...Vacuum exhaust pulp,
121...Base holder support member.

Claims (14)

[Claims] (1) A gaseous raw material for forming a deposited film, a gaseous halogen-based oxidizing agent having the property of oxidizing the raw material, and a gaseous substance containing as a component a component serving as a valence electron control agent. , a plurality of precursors including excited state precursors are generated by introducing and contacting them into the reaction space, and at least one of these precursors is used as a source of a deposited film component in the film forming space. A deposited film forming method characterized by forming an epitaxially deposited film with controlled valence electrons on a heated and maintained substrate. (2) The method for forming a deposited film according to claim (1), wherein the gaseous raw material is a chain silane compound. (3) The method for forming a deposited film according to claim (2), wherein the chain silane compound is a linear silane compound. (4) The deposited film forming method according to claim (3), wherein the linear silane compound is represented by the general formula Si_nH_2_n_+_2 (n is an integer from 1 to 8). (5) The method for forming a deposited film according to claim (2), wherein the chain silane compound is a branched chain silane compound. (6) The method for forming a deposited film according to claim (1), wherein the gaseous raw material is a silane compound having a silicon ring structure. (7) The method for forming a deposited film according to claim (1), wherein the gaseous raw material is a chain germane compound. (8) The deposited film forming method according to claim (7), wherein the chain germane compound is represented by the general formula Ge_mH_2_m_+_2 (m is an integer from 1 to 5). (9) The method for forming a deposited film according to claim 1, wherein the gaseous raw material is a germanium compound having a germanium ring structure. (10) The method for forming a deposited film according to claim (1), wherein the gaseous halogen-based oxidizing agent contains a halogen gas. (11) The method for forming a deposited film according to claim (1), wherein the gaseous halogen-based oxidizing agent contains fluorine gas. (12) The deposited film forming method according to claim (1), wherein the gaseous halogen-based oxidizing agent includes chlorine gas. (13) The method for forming a deposited film according to claim (1), wherein the gaseous halogen-based oxidizing agent is a gas containing fluorine atoms as a constituent component. (14) The component serving as the valence electron control agent is listed in Periodic Table I
Claim No. (2) which is an element belonging to Group II or Group V
1) Deposited film formation method described in section 1).