JP2010225792A - Film forming device and film forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a film forming device that forms a film having less deterioration associated with aging at a high speed by vapor phase growth, and to provide a film forming method. <P>SOLUTION: The film forming device 1 includes a plurality of decomposition chambers 10 and 20 wherein material gases different from each other are supplied and the supplied gases are selectively decomposed by different decomposition methods respectively to produce film-formation precursors contributing to the formation of film, and a film formation chamber 30 with which the plurality of decomposition chambers are independently connected and wherein a substrate is arranged inside, and the gases containing the film formation precursors that are produced by the decomposition chambers respectively are supplied to the substrate 40 arranged inside the film formation chamber, so as to form a film on the surface of the substrate. Preferably, a first material gas containing SiH<SB>4</SB>and a second material gas containing NH<SB>3</SB>are respectively supplied to form a silicon nitride film. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a film forming apparatus and a film forming method.

  In recent years, various electronic devices such as liquid crystal display devices, organic electroluminescence display devices, and X-ray imaging devices have been developed. When these electronic devices are manufactured, a thin film made of an inorganic material may be formed to ensure insulation and gas barrier properties.

  For example, in the case of manufacturing a field effect thin film transistor (TFT) as a switching element in a display device or an imaging device, an insulating film such as a gate insulating film or an interlayer insulating film is used in manufacturing an organic electroluminescence display device. In addition, it is necessary to form a protective film for protecting the organic electroluminescence element from moisture and oxygen with a thickness of the order of nm to μm by a silicon oxide film, a silicon nitride film, or the like.

  As a method for forming such a thin film, there is a chemical vapor deposition (CVD) method. One or more kinds of source gases are supplied onto the substrate, and a gas film is excited by a thermal energy, plasma discharge, light (laser, ultraviolet ray, etc.), a catalyst or the like to cause a chemical reaction to form a thin film on the surface of the substrate.

For example, when a silicon nitride film is formed by a CVD method, various factors such as an excitation method, a flow rate of a source gas, a temperature at the time of film formation, and a pressure affect the film quality.
In Patent Document 1, when a silicon nitride film is formed by plasma CVD using SiH ₄ , NH ₃ , and N ₂ as raw materials in order to form a silicon nitride film having a low hydrogen content, the decomposition rate of NH ₃ is within a certain range. It has been proposed to control.
Patent Document 2 proposes that the flow rate ratio (SiH ₄ / NH ₃ ) of the source gas is controlled within a certain range when the silicon nitride film is formed by the low pressure CVD method.

In Non-Patent Document 1, when a silicon nitride film is formed by catalytic chemical vapor deposition (Cat-CVD) using SiH ₄ and NH ₃ as source gases, SiH ₃ and NH ₂ are the main film formation precursors. It has been reported.
Further, Non-Patent Document 2 reports that when a SiN film is formed from SiH ₄ and N ₂ by plasma CVD, a good SiN film can be obtained by performing Xe lamp irradiation.

JP-A-8-274089 JP-A-6-120157 Material 55 (2006) 142 Japan Journal of Applied Physics 28 (1989) L2316

  An object of the present invention is to provide a film forming apparatus and a film forming method capable of forming a film with little deterioration with time change by vapor phase chemical growth.

  In order to achieve the above object, the following present invention is provided.

<1> A plurality of decomposition chambers that supply different source gases, and selectively generate the deposition precursors that contribute to film formation by selectively decomposing the supplied source gases by different decomposition methods. ,
The plurality of decomposition chambers are independently connected, and a film formation chamber in which a substrate is disposed,
A film is formed on the surface of the substrate by supplying a gas containing the film formation precursor generated in each of the plurality of decomposition chambers to a substrate disposed in the film formation chamber. Deposition device.
<2> as the plurality of decomposition chamber, a first raw material gas is supplied containing SiH _4, a first cracking chamber to produce SiH ₃ selectively decompose the SiH _4, the containing NH ₃ 2 source gas, and a second decomposition chamber for selectively decomposing NH ₃ to generate NH ₂ ,
The gas containing SiH ₃ generated in the first decomposition chamber and the gas containing NH ₂ generated in the second decomposition chamber are respectively supplied to the substrate disposed in the film formation chamber. Thus, the silicon nitride film is formed on the surface of the substrate. The film forming apparatus according to <1>.
<3> The film forming apparatus according to <2>, wherein the first decomposition chamber decomposes the SiH ₄ into SiH ₃ by an RF plasma method or a microwave plasma method.
<4> The composition according to <2> or <3>, wherein the second decomposition chamber decomposes the NH ₃ into NH ₂ by a UHF plasma method, a Cat-CVD method, or a photo-CVD method. Membrane device.
<5><1> to <4>, further comprising gas concentration measuring means for measuring the concentration of at least one gas around the substrate disposed in the film forming chamber. The film-forming apparatus in any one.
<6> The apparatus further comprises gas concentration control means for adjusting the concentration of the source gas supplied to each of the plurality of decomposition chambers based on the gas concentration measured by the gas concentration measuring means. <5> The film forming apparatus according to the above.
<7> A step of selectively decomposing a plurality of source gases different from each other by a different decomposition method for each source gas to generate a film formation precursor that contributes to film formation;
Forming a film on the surface of the substrate by supplying a gas containing the film-forming precursor generated for each source gas to the substrate, respectively.
<8> Before the step of selectively decomposing the plurality of source gases by different decomposition methods, the deposition precursor and the source gas are selectively decomposed to generate the deposition precursor. <7> The film forming method according to <7>, further comprising a step of specifying the decomposition method.
<9> As the plurality of source gases, a first source gas containing SiH ₄ and a second source gas containing NH ₃ are used, and the SiH ₄ contained in the first source gas is changed to SiH ₃ . By selectively decomposing NH ₃ contained in the second source gas into NH ₂ and supplying the gas containing SiH ₃ and the gas containing NH ₂ to the substrate, respectively, the surface of the substrate A silicon nitride film is formed on the film forming method according to <7> or <8>.
<10> The film forming method according to <9>, wherein the first decomposition chamber decomposes the SiH ₄ into SiH ₃ by an RF plasma method or a microwave plasma method.
<11> The film forming method according to <9> or <10>, wherein the NH ₃ is decomposed into NH ₂ by a UHF plasma method, a Cat-CVD method, or a photo CVD method.

  ADVANTAGE OF THE INVENTION According to this invention, the film-forming apparatus and film-forming method which can form the film | membrane with little deterioration accompanying a time-dependent change by vapor phase chemical growth at high speed are provided.

Hereinafter, the present invention will be specifically described with reference to the accompanying drawings.
Prior to the completion of the present invention, the present inventor conducted a molecular dynamics simulation analysis in order to find a gas phase chemical species capable of forming a silicon nitride film with little change over time. The relationship with the film quality was clarified and the gas phase reaction was examined.

As a result, the present inventor can, for example, combine a plurality of CVD methods with different energies to selectively decompose SiH ₄ into SiH ₃ and NH ₃ into NH ₂ and supply them to the surface of the substrate. It has been found that a silicon nitride film with a small amount can be formed at high speed.
Further, when forming a film as described above, the concentration of the source gas is adjusted by observing the concentrations of SiH ₃ , NH ₂ , and H in the vicinity of the substrate, so that deterioration due to change with time is small and nitriding is highly uniform It has also been found that the silicon film can be more reliably formed.

Based on these findings, in the present invention, first, a plurality of source gases are generated by decomposing each, and a plurality of deposition precursors that contribute to the formation of a target film and a source gas are selectively decomposed. The decomposition method for generating the film precursor is specified.
Regarding the identification of a plurality of film formation precursors that contribute to the formation of the target film, the correlation between the film formation precursor and the film structure can be clarified by molecular dynamics simulation. As for the method for producing the film formation precursor, a method suitable for decomposition is specified from the decomposition energy of the source gas. For example, in the case of plasma CVD, a general-purpose plasma simulator can identify a decomposition product from the decomposition energy of the plasma.

Specifically, Journal of Chemical Physics Vol. 115, NO. 14 (2001) pp. 6679-6690 H.R. Ohta et al .; Thin Solid Film 515 (2007) pp. 4879-4882. Using molecular dynamics simulation or Monte Carlo simulation disclosed in Taguchi et al., Etc., it is possible to accurately calculate the adhesion coefficient of gas phase species, the bond distance between atoms, energy, etc., and based on these calculated values, It is possible to specify (select) a deposition precursor that gives a highly uniform film with little deterioration due to change.
In addition, a general plasma simulator (see, for example, Applied Surface Science 192 (2002) 176-200) can specify a generation method that provides a desired film formation precursor.

  In this way, appropriate deposition precursors and decomposition methods that contribute to film formation are identified in advance through simulations, etc., and film formation precursors that contribute to film formation by selective decomposition using different decomposition methods for each source gas A film is formed on the surface of the substrate by supplying a gas containing a film-forming precursor generated for each source gas to the substrate. By such a method, a thin film with little deterioration with time can be formed at high speed.

In the present invention, “selectively decomposing source gas” does not mean that all source gas is decomposed into a desired film-forming precursor, but preferably at least part of the supplied source gas, preferably Means to decompose 40% or more, more preferably 60% or more, particularly preferably 80% or more into a desired film-forming precursor. Further, the present invention is not limited to the case where the source gas is decomposed only into a desired film formation precursor that contributes to film formation, and even if a part of the material gas is decomposed into a material different from the film formation precursor, This includes the case where the deposition precursor is supplied most to the substrate. For example, when a part of the source gas is decomposed into a material different from the desired film formation precursor, the material is consumed by a gas phase reaction, and only a film formation precursor is introduced into the substrate. Including.
In addition, the “different decomposition method” in the present invention specifically means that the energy distribution of the method of decomposing the raw material gas is different. For example, even in the same plasma method, the frequency, voltage, pressure, etc. If the energy distribution differs depending on the difference, it falls under “different decomposition methods”.
Hereinafter, a case where a silicon nitride film is formed will be described as an example.

(1) Identification (selection) of film precursor
(A) Evaluation of adhesion coefficient When forming a silicon nitride film, SiH ₃ and NHx (x = 0, 1, 2), which can be gas phase chemical species, are formed at 300 K using α-Si ₃ N ₄ as a substrate. The adhesion coefficient for each gas phase species when filmed was calculated from molecular dynamics simulation. Here, the simulation was performed by changing the composition ratio (SiH ₃ / NHx) of the incident molecules within the range of 0.33 to 3.0 and the incident energy within the range of 0.1 to 20 eV. The result is shown in FIG.

As shown in FIG. 1, although there are some variations depending on the composition ratio and the difference in incident energy even in the same gas phase chemical species, the average adhesion coefficients of SiH ₃ , N, NH, and NH ₂ are 0.33, 0,. The results of 73, 0.55, and 0.37 were obtained. A chemical species having a smaller adhesion coefficient has a longer surface diffusion and bonds at a stable site, so that it is considered that a thin film having excellent stability can be easily obtained. That is, with respect to NHx (x = 0, 1, 2) that can be a gas phase chemical species, it is considered that NH ₂ gives the most stable and stable film with little change with time in terms of the adhesion coefficient.

(B) Evaluation of N—H bond The N—H bond in the amorphous silicon nitride film (a-SiN: H film) is highly reactive and is thought to be deteriorated by oxidation or the like. For example, cracks are generated due to structural changes associated with the reaction, and the performance as a barrier film is lowered. Also, the conductive element is diffused into SiN through the cracks, so that the performance as an insulating film is also lowered. For this reason, it is considered that the smaller the N—H bonds in the formed film, the more the barrier property and the insulation can be prevented from lowering with time.

Therefore, the Si-H bond / N-H bond ratio of the a-SiN: H film prepared by simulation using SiH ₃ and NHx (x = 0, 1, 2) is expressed as a radial distribution function (RDF). ). 2 (A) to 2 (C) are respectively evaluated for films having the same hydrogen content and Si / N ratio in the film with respect to SiH ₃ and NHx (x = 0, 1, 2) that can be gas phase chemical species. It is a thing.
From the results of this simulation, with respect to the nitrogen component, NH _{2 is} the least when NH ₂ is used among N, NH, and NH _2. Therefore, it is barrier property to use NH ₂ as a film formation precursor. In addition, it is considered that a film with little decrease in insulation can be obtained.

(2) Identification (selection) of decomposition method
From the calculation results of the adhesion coefficient and N—H bond, SiH ₄ to SiH ₃ and NH ₃ to NH ₂ are selectively decomposed and generated to form a silicon nitride film with little deterioration with time. I think it can be done.
Here, the decomposition energies of SiH ₄ , NH ₃ , and H _{2 that} are source gases are as follows.

(A) from decomposition techniques relationship such degradation energy to SiH ₃ from SiH _4, To selectively produce SiH ₃ from SiH _4, decomposing SiH ₄ in the energy to less than 8.8 eV 9.5EV It is preferable to preferentially generate SiH ₃ .
For example, such selective generation is possible in CVD that can specify decomposition energy such as photo-CVD, but there is an industrial problem that the film formation rate is slow.

  3A and 3B schematically show examples of energy distributions of plasma enhanced chemical vapor deposition (PE-CVD), respectively. Although the energy distribution varies depending on the frequency, voltage, pressure, etc., an ultra high frequency (UHF) plasma usually has an energy distribution with a large proportion of low electron energy as shown in FIG. As shown in FIG. 3B, the type plasma (ICP: Inductively Coupled Plasma) has an energy distribution with a large proportion of high electron energy (Samukawa, “The Journal of Plasma and Fusion Research” 77 (2001) 666- See page 667).

The ICP shown in FIG. 3B has a peak between 5 and 10 eV and has a broad energy distribution up to about 50 eV. Therefore, when SiH ₄ is decomposed with such high energy plasma, the primary SiH ₂ or the like may be generated as a decomposition product. However, SiH ₂ has a very high reaction probability in the gas phase, is easily consumed by the gas phase chemical reaction, and is considered to contribute little to the film formation. For this reason, there is little correlation between increasing the plasma energy and the deposition precursor, and it is desirable to use high-energy plasma in order to increase the deposition rate with respect to decomposition of SiH ₄ . That is, high energy plasma (RF plasma method or microwave plasma method) such as ICP is suitable for decomposition of SiH ₄ .

The same applies to H ₂ , and since decomposition energy does not contribute to the film formation precursor, it is possible to generate H atoms at a high concentration by decomposition with high energy plasma. Maintaining H at a high concentration is considered to be important in forming an a-SiN film with little change over time.

Decomposing scheme whereas in (b) from NH ₃ to NH _2, To selectively produce NH ₂ from NH _3, the relationship of the decomposition energy, the NH ₃ with an energy of less than 4.5eV 8.3eV It is preferable to decompose and generate NH ₂ preferentially. Therefore, it is preferable to decompose NH ₃ into NH ₂ by a technique in which the peak of the energy distribution appears at a lower energy than the technique used for the decomposition of SiH ₄ .
Here, the reaction rate constant between the NHx-based radical and the source gas (SiH ₄ , NH ₃ , H ₂ ) is, for example, as shown in Table 2 according to the following documents (1) to (6).
(1) A. Tezaki, et al., J. Phys. Chem., 99 (1995) 1466
(2) V. Ya. Basevich, Khim. Fiz., 7 (1998) 1552
(3) C. Zetzsch, et al., Ber. Bunsenges. Phys. Chem., 85 (1981)
(4) RZ Pascual, et al., J. Phys. Chem. A, 106 (2002) 4125
(5) A. Fontiji, et al., Combust. Flame, 145 (2006) 543
(6) AM Mebel, et al., J. Mol. Struct. THEOCHEM, 461 (1999) 223

The smaller the reaction rate constant, the easier it is to reach the substrate and contribute to film formation. However, the reaction rate constants of the NHx radicals are all 10 ⁻¹³ or less, and N, NH, which are primary decomposition products from NH ₃ , NH ₂ has a relatively low reaction probability in the gas phase, and is considered to reach the substrate before the gas phase reaction. Therefore, it is not appropriate to use a high energy plasma for the decomposition of NH ₃ and relatively increase the concentration of N or NH. Therefore, for example, it is preferable to selectively generate NH ₂ at a high concentration by using UHF plasma with low energy and small energy dispersion as shown in FIG.

From the above evaluation and examination results, SiH ₄ is selectively decomposed by ICP to generate SiH ₃ , and NH ₃ is selectively decomposed by UHF plasma method to generate NH ₂ and supplied to the substrate. Thus, it is presumed that a silicon nitride film with little deterioration accompanying a change with time can be formed at high speed by vapor phase growth. NH ₃ can be selectively decomposed into NH ₂ by Cat-CVD or photo-CVD, which is preferable.

<Silicon nitride film deposition system>
Next, an apparatus for forming a film by selectively decomposing each source gas as described above will be described.
FIG. 4 shows an example of the configuration of a silicon nitride film deposition apparatus according to the present invention. The film deposition apparatus 1 according to the present embodiment includes a first decomposition chamber 10 that selectively decomposes SiH ₄ into SiH ₃ , a second decomposition chamber 20 that selectively decomposes NH ₃ into NH ₂ , The first decomposition chamber 10 and the second decomposition chamber 20 are independently connected to each other, and the film formation chamber 30 in which the substrate 40 is disposed is provided. Then, the gas containing SiH ₃ generated in the first decomposition chamber 10 and the gas containing NH ₂ generated in the second decomposition chamber 20 are respectively supplied to the substrate 40 disposed in the film forming chamber 30. As a result, a silicon nitride film is formed on the surface of the substrate 40.

-First decomposition chamber-
First cracking chamber 10, a first raw material gas is supplied containing SiH _4, selectively degrades the SiH ₄ to SiH ₃ by ICP method.
A main body 12 made of a quartz tube is provided with a gas inlet 14 for introducing a first source gas containing SiH _4, and a gas concentration control means 13 for adjusting the concentration of the source gas is provided outside. Yes.

  A high-frequency application electrode (antenna) 16 connected to a high-frequency power source is spirally arranged around the main body 12 and connected to the RF high-frequency power source 11. The shape and arrangement of the electrode (antenna) 16 may be set as appropriate.

-Second decomposition chamber-
Second decomposition chamber 20, the second source gas is supplied containing NH _3, selectively degrades the NH ₃ to NH ₂ by UHF plasma. The main body 22 is provided with a gas inlet 24 for introducing a second source gas containing NH _3, and a gas concentration control means 23 for adjusting the concentration of the source gas is provided outside.

  The upper part of the second decomposition chamber 20 is a quartz window 27, and an electrode (antenna) 26 is installed outside thereof. The electrode 26 is connected to the high-frequency power source 21, and plasma is generated at a UHF band frequency. The shape and arrangement of each electrode (antenna) 26 in the second decomposition chamber 20 may be set as appropriate.

−Deposition chamber−
In the film formation chamber 30, the first decomposition chamber 10 and the second decomposition chamber 20 are independently connected. The gas containing SiH ₃ generated in the first decomposition chamber 10 and the gas containing NH ₂ generated in the second decomposition chamber 20 are respectively supplied into the film forming chamber 30 by gas transport and diffusion. The central axes of the first decomposition chamber 10 and the second decomposition chamber 20 are directed toward the support table 32 so that the released gases can easily come into contact with the substrate 40 arranged on the support table 32. It has been.

  Inside the film forming chamber 30, a support base 32 is provided in the vicinity of the first decomposition chamber 10 and the second decomposition chamber 20 to support the substrate 40 at a position approximately equidistant from each decomposition chamber 10, 20. ing. The support base 32 can be rotated via a rotating shaft 34 by a motor (not shown). The substrate 40 is fixed to the support base 32 so that the substrate 40 does not fall off when the support base 32 is rotated. The fixing means is not particularly limited, and may be fixed mechanically or by an electrostatic chuck.

The support base 32 is connected to the high frequency power supply 31. The high-frequency power source 31 is controlled independently from the high-frequency power sources 11 and 21 that generate plasma in the first decomposition chamber 10 and the second decomposition chamber 20, respectively.
Further, a gas concentration measuring means 38 for measuring the concentration of at least one kind of gas around the substrate 40 is provided near the support base 32.

  An exhaust port 36 for exhausting gas from the film formation chamber 30 is provided at the bottom of the film formation chamber 30. The exhaust port 36 is connected to a vacuum pump (not shown) for decompression.

<Method for forming silicon nitride film>
Next, a method for forming a silicon nitride film on the surface of the substrate 40 using the film forming apparatus 1 of the present embodiment will be described.
First, a substrate 40 on which a silicon nitride film is formed is prepared. The substrate 40 may be selected according to a device (semiconductor device, display device, imaging device, etc.) to be finally manufactured, or may be a substrate in a manufacturing process in which another film or the like is already formed.

For example, when manufacturing an organic electroluminescence display device, a substrate made of an inorganic material such as zirconia-stabilized yttrium oxide (YSZ) or glass is suitable. In addition, when it is not necessary to extract light from the substrate side, for example, a metal substrate such as stainless steel, Fe, Al, Ni, Co, Cu, or an alloy thereof can be used.
On the other hand, when manufacturing a semiconductor device, a semiconductor substrate such as Si can be used.

  Moreover, in this embodiment, since any source gas is decomposed | disassembled and formed into a film by plasma CVD, it can form into a film at low temperature compared with thermal CVD. Therefore, using polyester films such as polyethylene terephthalate, polybutylene phthalate and polyethylene naphthalate, resin films such as polystyrene, polycarbonate, polyethersulfone, polyarylate, polyimide, polycycloolefin, norbornene resin, poly (chlorotrifluoroethylene), etc. Also good.

After fixing the surface of the substrate 40 opposite to the side on which the film is formed toward the support base 32, the inside of the film forming chamber 30 is decompressed through the exhaust port 36. Then, while rotating the support base 32 in a predetermined direction, the first decomposition chamber 10 contains the first source gas containing NH ₃ and Ar, the second decomposition chamber 20 contains SiH ₄ , H ₂ , and A second source gas containing Ar is supplied.
The pressure in each of the decomposition chambers 10 and 20 and the film formation chamber 30, the substrate temperature, the flow rate of the source gas, and the like depend on the purpose of the silicon nitride film to be formed, the material of the substrate, and the like. 1.0 to 100 Pa, substrate temperature: 100 to 400 ° C., SiH ₄ / NH ₃ flow rate ratio: set to 0.5 to 2.0.

In the first decomposition chamber 10, a first source gas is supplied, and a high frequency of, for example, 27 MHz is applied to the coil (antenna). Thereby, SiH ₄ contained in the first source gas is selectively decomposed into SiH ₃ and H by ICP plasma.
On the other hand, in the second decomposition chamber 20, a second source gas is supplied and, for example, an ultra-high frequency of 500 MHz is applied. Thereby, NH ₃ contained in the second source gas is selectively decomposed into NH ₂ and H by the UHF plasma.

The gas containing SiH ₃ and H generated in the first decomposition chamber 10 and the gas containing NH ₂ and H generated in the second decomposition chamber 20 are supplied into the film forming chamber 30 by gas transport and diffusion, respectively. The The gases introduced from the decomposition chambers 10 and 20 into the film forming chamber 30 are held on the support base 32, mixed on the rotating substrate 40 and in contact with the surface of the substrate 40. Thereby, a silicon nitride film is formed on the surface of the substrate 40 by a gas phase chemical reaction.

At the time of film formation, it is preferable to measure the concentrations of gases near the substrate 40 such as SiH ₃ and NH ₂ by the gas concentration measuring means 38. Based on the measured concentrations of SiH ₃ and NH ₂ , the concentration of SiH ₄ supplied to the first decomposition chamber 10 by the gas concentration control means 13, 23 and the concentration of NH ₃ supplied to the second decomposition chamber 20. Adjust each concentration. Thus, if the concentration of the source gas supplied by measuring the concentration of the film-forming precursors (SiH ₃ and NH ₂ ) in the vicinity of the substrate is adjusted, the change with time is small and the uniformity of the composition and the film thickness is high. The SiN: H film can be formed more reliably.
Note that the concentration ratio of SiH ₄ and NH ₃ may be adjusted by adjusting the flow rate of each raw material gas, or the concentration of SiH ₄ contained in the first raw material gas, or contained in the second raw material gas. The concentration of NH ₃ may be adjusted.

The source gas may be adjusted manually, but automatic control may be performed by linking the gas concentration measuring means 38 and the gas concentration control means 13, 23. For example, if the concentration of the raw material gas is adjusted by automatically feeding back the measured values of SiH ₃ and NH ₂ by the gas concentration measuring means 38 to the gas concentration control means 13 and 23, a-SiN: The H film can be more reliably and easily formed.
By combining a plurality of plasma CVD methods in this manner and controlling the decomposition energy for each source gas and selectively decomposing it to generate a film-forming precursor, a high-quality a-SiN: H film can be formed at high speed. It becomes possible.

As mentioned above, although this invention was demonstrated, this invention is not limited to the said embodiment.
For example, the frequency of each high frequency power source may be set as appropriate. The method for decomposing each source gas is not limited to the plasma method described in the embodiment, and may be specified and selected according to the type of source gas and the film to be formed. For example, capacitively coupled plasma (CCP), electron cyclotron resonance plasma (ECR), helicon wave-excited plasma (HWP), microwave-excited surface wave S Various plasma methods such as Plasma) may be used. In addition, the source gas may be decomposed by light, heat, or the like, not limited to plasma decomposition.

  The film formed according to the present invention is not limited to a silicon nitride film, and can be applied to the formation of other inorganic films or organic films formed by a vapor phase chemical growth method using a plurality of source gases. Further, the function of the film is not particularly limited, and the present invention can be applied to the formation of a semiconductor film or a conductive film, for example.

Is a diagram showing the attachment coefficient of the composition ratio and SiH ₃ was calculated from the molecular dynamics simulation varying the incident energy and NHx (x = 0,1,2). It is the figure which evaluated the Si-H bond / NH bond ratio of the a-SiN: H film | membrane calculated from the molecular dynamics simulation with the radial distribution function. (A) When N is used (B) When NH is used (C) When NH ₂ is used It is a figure which shows roughly the example of the energy distribution of a plasma chemical vapor deposition method. (A) UHF plasma energy distribution (B) ICP energy distribution It is the schematic which shows an example of a structure of the film-forming apparatus which concerns on this invention.

DESCRIPTION OF SYMBOLS 1 Film-forming apparatus 10 1st decomposition chamber 11 High frequency power supply 12 1st decomposition chamber main body 13 Gas concentration control means 14 Gas inlet 16 Electrode (antenna)
20 Second decomposition chamber 21 High-frequency power source 22 Second decomposition chamber body 23 Gas concentration control means 24 Gas inlet 26 Electrode (antenna)
27 Quartz window 30 Deposition chamber 31 High frequency power source 32 Support base 34 Rotating shaft 36 Exhaust port 38 Gas concentration measuring means 40 Substrate

Claims (11)

A plurality of decomposition chambers that supply different source gases, and selectively generate the deposition precursors that contribute to film formation by selectively decomposing the supplied source gases by different decomposition methods,
The plurality of decomposition chambers are independently connected, and a film formation chamber in which a substrate is disposed,
A film is formed on the surface of the substrate by supplying a gas containing the film formation precursor generated in each of the plurality of decomposition chambers to a substrate disposed in the film formation chamber. Deposition device. As the plurality of decomposition chamber, a first raw material gas is supplied containing SiH _4, a first cracking chamber to produce SiH ₃ selectively decompose the SiH _4, a second source containing NH ₃ A second decomposition chamber that is supplied with gas and selectively decomposes NH ₃ to generate NH ₂ ;
The gas containing SiH ₃ generated in the first decomposition chamber and the gas containing NH ₂ generated in the second decomposition chamber are respectively supplied to the substrate disposed in the film formation chamber. The film forming apparatus according to claim 1, wherein a silicon nitride film is formed on the surface of the substrate. The film forming apparatus according to claim 2, wherein the first decomposition chamber decomposes the SiH ₄ into SiH ₃ by an RF plasma method or a microwave plasma method. 4. The film forming apparatus according to claim 2, wherein the second decomposition chamber decomposes the NH ₃ into NH ₂ by a UHF plasma method, a Cat-CVD method, or a photo-CVD method.   5. The apparatus according to claim 1, further comprising a gas concentration measuring unit that measures a concentration of at least one gas around the substrate disposed in the film forming chamber. The film forming apparatus according to item.   6. The apparatus according to claim 5, further comprising gas concentration control means for adjusting the concentration of the raw material gas supplied to each of the plurality of decomposition chambers based on the gas concentration measured by the gas concentration measuring means. 2. The film forming apparatus according to 1. A step of selectively decomposing a plurality of different source gases by a different decomposition method for each source gas to generate a film formation precursor that contributes to film formation;
Forming a film on the surface of the substrate by supplying a gas containing the film-forming precursor generated for each source gas to the substrate, respectively.   Prior to the step of selectively decomposing the plurality of source gases by different decomposing methods, the decomposing method for generating the film forming precursor by selectively decomposing each of the film forming precursor and the source gas. The film forming method according to claim 7, further comprising the step of specifying: As the plurality of source gases, a first source gas containing SiH ₄ and a second source gas containing NH ₃ are used, and the SiH ₄ contained in the first source gas is changed to SiH ₃ . of the NH ₃ contained in the raw material gas are selectively decomposed into NH _2, by supplying the gas containing the NH ₂ and gas containing SiH ₃ to each of the substrate, silicon nitride on the surface of the substrate The film forming method according to claim 7 or 8, wherein a film is formed. The film forming method according to claim 9, wherein the SiH ₄ is decomposed into SiH ₃ by an RF plasma method or a microwave plasma method. 11. The film forming method according to claim 9, wherein the NH ₃ is decomposed into NH ₂ by a UHF plasma method, a Cat-CVD method, or a photo-CVD method.

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