JPS63222422A - Formation of deposited film - Google Patents

Abstract

PURPOSE:To form a high quality deposited film uniformly over a large area, by introducing active species through a wide introducing port with respect to a film forming space, and introducing a precoursor through a plurality of introducing ports, which are arranged in the vicinity of the active species introducing port. CONSTITUTION:A substrate 103 is mounted on a supporting stage 102. The inside of a film forming chamber 101 is exhausted and the pressure is reduced. Thereafter, raw material gas is excited in an infrared-ray image furnace 109 through a raw material gas feeding pipe 108. Thus a precoursor is formed and discharged into a meeting part D through multiple nozzles 111. Meanwhile active species forming gas is supplied into a decomposing space C through a nozzles 114 through a gas feeding pipe 113. Plasma is yielded in a plasma chamber 117 with a microwave from a microwave guide 115. Then the active species are yielded in the chamber 117. The active species are sufficiently spread in the chamber 117 and made uniform. The active species are made to react with the precoursor of the raw gas, which is discharged through the nozzles 111, at the meeting part D. Thus a desired deposited film is formed on the substrate 103 in the film forming space A.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to deposited films, especially functional films, particularly semiconductor devices, photoelectric energy converters (solar cells).

For forming amorphous (including so-called microcrystalline), polycrystalline, non-single-crystalline or single-crystalline deposited films used in photoreceptor drums, image sensors, etc.) or photovoltaic elements. This invention relates to a method suitable for

[Conventional technology]

Various CVD methods such as plasma CVD method, photo CVD method, vacuum evaporation method, reactive sputtering method, ion blating method, etc. have been attempted to form silicon (Si) films at low temperatures. The plasma CVD method is widely used and commercialized.

Most of the deposited films obtained by the plasma CVD method are amorphous silicon (a-81), which has better optical characteristics, fatigue characteristics due to repeated use, uniformity, and mass productivity. There is room to improve overall characteristics. Furthermore, with the plasma CVD method, it is difficult to deposit a high quality polycrystalline silicon (polysilicon) film on a glass substrate at a low temperature.

The reaction process in forming silicon deposited films using the conventionally popular plano-r CVD method is considerably more complex than that of the conventional CVD method, and there are many aspects of the reaction mechanism that are unclear. . In addition, there are many formation parameters for the deposited film (for example, substrate temperature, flow rate and ratio of introduced gas, pressure during formation, high frequency power, structure of electrode structure 2 reaction vessel, and pumping speed).

Due to the combination of these many parameters (plasma generation formula, etc.), the plasma sometimes becomes unstable, which often has a significant adverse effect on the deposited film formed. Moreover, it is necessary to select device-specific parameters for each device, making it difficult to generalize manufacturing conditions.

As mentioned above, plasma CVD has many unclear points regarding the reaction mechanism.
As an alternative to the gold deposition method, multiple gases are introduced into the gold deposition space, and some of the gases are activated in advance with energy such as light heat or plasma, and the film is deposited on the substrate placed in the deposition space. HR-CV'D has been proposed. According to this invention, for example, when forming an amorphous silicon (a-81) film, SiF2 gas as a precursor and H* (hydrogen radicals) as an active species are combined. At least a-
81 is used.

In particular, the advantage of this method is that, depending on the concentration of H*, it is possible to produce anything from a Si film containing a microcrystalline phase, which is an amorphous form, to polycrystalline St (poly-8i).

However, in the conventional HR-CVD method, as shown in Figure 3, it is difficult to obtain a uniform film because the precursor and active species are created and associated in separate spaces, and the lifetimes of the precursor and active species are different. Met. As described above, it is strongly desired to develop a method for forming a deposited film that can be easily mass-produced while maintaining its practically usable characteristics and uniformity in the formation of silicon films obtained at low temperatures.

This applies not only to the a-81 film but also to other non-monocrystalline Si films and other non-single-crystalline or nested crystalline functional films, such as silicon nitride films, silicon carbide films, and silicon oxide films. The same can be said of the silicon dalmanium film (81-Go) and the like.

[Problems to be solved by the invention]

The present invention improves the characteristics of the film formed, the film formation speed, the reproducibility, and makes the film quality uniform, while being suitable for increasing the area of the film, improving film productivity, and facilitating mass production. The purpose of this invention is to provide a method for forming a deposited film that can achieve the following.

[Means for solving problems]

In the deposited film forming method of the present invention, a precursor serving as a raw material for forming a deposited film, which is generated in an activation space (B), is placed in a film forming space (4) for forming a deposited film on a substrate. In the deposited film forming method of forming a deposited film on the substrate by completely introducing the active species generated in the activation space C) and interacting with the precursor, the active species is By introducing the precursor into the film forming space through an introduction port having a wide cross section, and introducing the precursor through a plurality of introduction ports distributed in an introduction pipe arranged near the introduction port of the active species. , is characterized by forming a deposited film.

The present invention will be explained in detail below.

In the method of the present invention, before the raw materials for forming a deposited film are associated, they are activated by absorption of energy such as discharge energy, thermal energy, light energy, etc., or by chemical interaction such as catalytic action. It is characterized by That is, it contains active 81 gold that has been activated in advance and performs film deposition.

The term "precursor" as used in the present invention refers to anything that can be used to form a deposited film. "Active species" are those that chemically interact with the precursor to provide energy to the precursor, or chemically react with the precursor to form a deposited film more efficiently. It refers to something that has the role of making things possible.

Therefore, as an active species, it becomes a constituent element constituting the deposited film to be formed! ! It is acceptable to include a combination of components, or it is acceptable to not include such components.

In CVI, which normally uses active species, a precursor containing halodane or Fi/hydrogen, which is a raw material for forming a deposited film, chemically reacts with a raw material gas for forming a deposited film, or chemically reacts with the precursor. Active species are used. CVN 1, in which hydrogen radicals (・H) play an important role as active species.
kHR-CVI).

In the present invention, the raw material gas for forming a deposited film containing halogeno and/or hydrogen in its molecules used for film formation includes a compound having silicon as its main skeleton, a compound having carbon as its main skeleton, and germanium. Main skeleton compound and hydrogen,
Examples include fluorine, chlorine, hydrogen fluoride, chlorine fluoride, and hydrogen chloride.

These compounds may be used alone or in combination as appropriate.

As a compound having silicon as a main skeleton, a compound in which part or all of the hydrogen atoms of a chain or cyclic silane compound is replaced with a halogen atom, for example, is used as dl, and specifically, for example,
Chain silicon halide, 5tvy2. (Ma is an integer of 3 or more, Y has the above-mentioned meaning.) Cyclic silicon halide,
81uHiYa (U and y have the above meanings. x
+y=2u or 2u+2. ), and the like.

Specifically, for example, 5ir4. (5iF2)5. (S
iF'2) 6° (5IF2) 4.81□F6. St.
F8.5iHF, I5IH2F2゜5ICL4.
(5iCt2), , 5lur4# (5iBr2)
5゜812CA6.812Br6.5iHC2,,5i
HBr, , 81HI, .

Examples include those in a gaseous state or those that can be easily gasified, such as S1□Ct3V3.

These silicon compounds may be used alone or in combination of two or more.

Further, as a compound having carbon as a main skeleton, for example, a compound in which part or all of the hydrogen atoms of a chain or cyclic hydrocarbon compound is replaced with a halogen atom is used.
For example, C1Y2u+2 (" is an integer greater than or equal to 1, Y is F
#Ct a Br and at least one element selected by engineering. ) chain halogenated carbon “v”
Cyclic silicon halide represented by Y2v (ma is an integer of 3 or more, Y has the above meaning), CuHxY
U and Y have the meanings given above. X+7=2u or 2u
+2. ), and the like.

Specifically, for example, CF4. (CF2)5. (CF
2) 6° (CF2)4. C2F61C, F81C
HF5jCH2F2. CC14m (CCt'2)5
* CBr4 (CBr2)5 * C2C26m C2
Br, 6 #CHCt, , CHI, , C2CL
Examples include those in a gaseous state or those that can be easily gasified, such as 3F.

These carbon compounds may be used alone or in combination of two or more.

Further, as a compound having germanium as a main skeleton, for example, a compound in which a part or all of the hydrogen atoms of a chain or cyclic germanium hydride compound is replaced with a halogen atom is used, and specifically, for example, G・uY2u+2 (" is an integer greater than or equal to 1, Y is F, ct.

At least one element selected from Br and l. ) Chained dalmanium halide Go, Y2
Cyclic germanium halide represented by v (ma is an integer of 3 or more, Y has the above-mentioned meaning), G@uH! YA (U and Y have the meanings given above.

x+y=2u or 2u+2. ), and the like.

Specifically, for example, GeF4 = (GeF2)5 #
(G6F2)6=CGeF2)4 e Ga2Fb e
Ge3F6- G@'HF5 # GeH2F2-G
aCl2 (GaCA2)5 # GaBr4 s (
GaBr2), #Go2Ct6°Go2Br6.
GaHC2, , GaHBr, , GeHI3, G
Examples include those that are in a gaseous state or can be easily gasified, such as e2Ct3F3.

The deposited film formed by the method of the present invention can be doped with an impurity element during or after film formation.

The impurity element to be used is, as a p-type impurity, an element in group A of the periodic table, such as B @ At m Ga.
Preferred examples include s In * Tt, and n
Type impurities include elements in group V A of the periodic table, such as P.
#As @ Sha B1 etc. are preferred, and ha a P #8b etc. are particularly optimal. The amount of impurities to be doped is appropriately determined depending on desired electrical and optical characteristics.

The substance containing such an impurity element as a component (substance for introducing impurities) is a compound that is in a gaseous state at room temperature and normal pressure, or at least in a gaseous state under deposited film forming conditions, and that can be easily vaporized with an appropriate vaporization device. It is preferable to select Such compounds include PH5-P2H4*P
F5- PF5 #PCl5 #AsH3, AaF,
*AaF5. AsC2g, SbH3, SbF
, .

HF5 = BCt5- BBr3# B2H4s B
4H1o e B5HF eB5H11e BbHl.

'　B6H12 etc. can be mentioned.

The compounds containing impurity elements may be used alone or in combination of two or more.

The compound containing an impurity element as a component may be introduced into the film forming space directly in a gaseous state or mixed with a film forming raw material gas.

In order to generate active species, hydrogen, halogen compounds (e.g. F2 gas, ct2if gas, gasified Brz, gasified I2, HF gas, HCt gas, gasified HBr) are used.
, x6F'-, etc.), and if necessary, an inert gas (He*Ar#N
e a Krm This is done by

The present invention is characterized in that when the active species obtained in the activation space (Q) is introduced into the film forming space (4), it is introduced in a wider area than in the past. As shown in the figure, use a thin tube of about 40 to 50 mm diameter to
The metal was introduced into the gold film forming space (4), but with this method, the range in which the quality uniformity of the deposited film produced was maintained was as small as about 20 φ. The main reason for this is that when the active species of He touches the wall surface, it is inactivated into species that cannot contribute to the chemical reaction at the association part (2). On the other hand, the raw material gas and/or the decomposition product of the raw material gas (1) and the precursor that is the raw material for forming the seed film generally has a longer lifespan than the active species mentioned above, so it is not necessary to route it through narrow pipes. can exist stably. Precursors such as SiF2 are sufficiently stable! Even when it was discharged into a vacuum from a nozzle of 70.51111φ, there was no change in quality. However, care must be taken as there is a possibility of polymerization if the temperature inside the pipe is low. Therefore, using a multi-nozzle, the raw material gas and/or the precursor are uniformly distributed in the meeting area (b) and the film forming space (
4).

That is, in the present invention, by introducing active species into the film forming space over a wide area and introducing raw material gases and/or precursors through a plurality of nozzles, uniform association can be achieved and uniform film quality can be achieved. A deposited film is formed.

It is necessary to uniformly spread the activated species over as wide an area as possible, and for this purpose it is desirable that the cross-sectional area of the outlet of the activation space (B) is at least as large as or larger than the area of the substrate. Further, it is preferable that the object does not collide with other obstacles until it collides with the precursor.

The introduction port of the precursor is preferably 0.055w*φ or more and 2■φ or less, and the meeting! It is better to arrange as many as possible so that the @ pressure does not exceed 10 Torr. More preferably, it is easier to obtain a uniform film if the pressure at the meeting portion (b) is 10 Torr or less.

In the present invention, activation energy is applied to the activation space (B) and the activation space (Q to generate precursors or active species. The excitation energy is DC, R
Furthermore, discharge energy by microwaves, thermal energy, original energy, and energy beams (laser beams, X-rays, electron beams, molecular beams, etc.) that can be converted into thermal energy can be used. Further, a precursor is generated by imparting energy of the generated active species or excited species generated by electric discharge or the like, or energy of electrons, ions, etc. to the raw material gas. That is, the activation space (B) and the meeting space (B) may exist in the same space.

Note that the precursors and/or active species generated from the raw material gas for film formation are usually obtained by applying energy (externally), but a catalytic reaction may be used as a form of energy application. An example of this will be explained below.

As a means of activating molecules containing halogens and/or hydrogen, they can be activated catalytically on a heating element made of a transition metal at a temperature lower than the thermal decomposition temperature of ordinary gases.

The transition metal that becomes the heating element used in the present invention is as follows:
It is desirable to select materials that are unlikely to be mixed into the deposited film due to sublimation, scattering, etc., and when activating using these materials, it is necessary to select activation conditions that will prevent these materials from entering the deposited film.

Such materials include those from period 4 or 5 of the periodic table.
Mention may be made of metals and alloys in the elements of the period and the sixth period, and among these, ①, v.

Transition metals belonging to groups (1), (2), and (2) can be suitably used.

Specifically, for example, Ti jNd * Cre Mo
* W eF'@ # Ni # Co * Rh
* Pd m Mn * Ag * Zn # Cd
Examples include ePd-Ag and Ni-Cr.

Further, in the present invention, the heating temperature of the heating element made of a transition metal provided in the film forming space is preferably 100°C to 30°C.
00°C, more preferably 200°C to Mo*Aus
Ir # Nb * Ta # V e Ti a P
Metals such as t#Pd or alloys thereof are commonly used.

The present invention will now be described with reference to a typical example of a PIN type diode device utilizing a 9A-81 deposited film doped with an impurity element formed by the method of the present invention.

FIG. 4 is a schematic diagram for explaining a configuration example of a typical PIN base diode device obtained by the present invention.

In the figure, 401 is a base, 402 and 407 #i thin film electrodes,
403 is a semiconductor film made of amorphous silicon a-81 (H,
X) layer 404, an amorphous silicon a-81 (H, X
) layer 405, amorphous silicon a-31 (H,X) layer 40 containing p-type hydrogen atoms and/or halogen atoms
Consisting of 6. 408 is a conductive wire connected to an external electric circuit device.

The base 401 may be conductive, anti-conductive, or electrically insulating. When the base 401 is conductive,
The thin film electrode 402 may be omitted. As the anti-conductive substrate, for example, 81 e GetGaAs e Zn
Examples include semiconductors such as O*Zn8. Thin film electrode 402
．． 407 is, for example, NiCr*A-1*Cr
s Mo # Au a Ir # Nb a Ta
*V*T1#Pt ePd, In2O
, I SnO2# It is obtained by providing a thin film of ITO (In2O, +5nO2) or the like on the substrate 401 by a process such as vacuum deposition, electron beam deposition, or splattering. The film thickness of the electrodes 402 and 407 is preferably 3
0~5X10'X, more preferably 100~5X103
It is desirable that the

In order to make the film body constituting the semiconductor layer of a7si (H-X) n-type or p-type as necessary, when forming the layer, an n-type impurity, a p-type impurity, or both impurities are added among the impurity elements. It is formed by doping the layer into the formed layer in a controlled amount.

To form n-type, l-type and p-type a-8T (H,X) layers or 1-type a-81:Ge (H=X) layer,
According to the method of the present invention, a gas of a compound containing silicon and a halogen and, if necessary, a gas of a compound containing hydrogen gas and an impurity element as a component or a gas of a compound containing an alloy element such as rumanium as a component is introduced into the film forming space. These introduced raw material gases come into contact with a heating element made of a transition metal and are activated by a thermal dissociation reaction, forming a deposited film on the substrate 401.

The layer thickness of the n-type and p-type a-8t(H,X) layers is preferably 100 to 10'l, more preferably 3
A range of 00 to 2000X is desirable.

In addition, type 1 凰-8t(H,X) layer or 凰-8l:G
The thickness of the ss (H,X) layer is preferably 50
0-10'X, preferably 1000-10000X
A range of is desirable.

〔Example〕

The present invention will be explained in more detail by giving specific examples below.

Example 1 Using the apparatus shown in Figure 1, 5t was produced by the following operations.
A (u, x) deposited film was formed.

In Figure 1, 101 is a film forming chamber, and a desired substrate 103 is placed on a substrate support stand 102 inside the film forming chamber.

Reference numeral 104 denotes a heater for heating the substrate, which is supplied with electricity via a conductive wire 105 and generates heat. The heater 104 heats and heats the substrate 103 before film formation, performs annealing treatment to further improve the properties of the formed film after film formation, and heats the substrate 103t during film formation as necessary. -Used in heating.

In carrying out the entire method of the present invention, when the entire substrate is heated, the heating temperature of the substrate is preferably 30 to 450°C, more preferably 50 to 350°C. 10
6 is a thermocouple for monitoring temperature.

Reference numeral 107 is connected to an exhaust system, and can be exhausted by a turbo molecular pump, a mechanical booster pump, or a rotary pump (not shown).

Reference numeral 108 denotes a raw material gas supply pipe, which is not shown in the figure, but supplies various raw material gases and, if necessary, carrier gas to each mass flow controller 9-! It is controlled and supplied at the desired flow rate. The raw material gas is excited in the infrared imaging furnace 109 to generate a precursor, that is, the tube inside the furnace 109 forms a decomposition space (B) for the raw material gas. The raw material gas containing the precursor passes through the precursor transport pipe 110t and is discharged from the multi-nozzle 111 having a plurality of nozzles to the meeting part (2). Note that some of the precursors, such as SiF2, are easily polymerized at low temperatures, so it is desirable to heat the precursor transport pipe 110t with the heater 112 (approximately 100° C.).

Reference numeral 113 is a supply pipe for active species generation gas and, if necessary, excitation and/or carrier gas.Although not shown in the figure, each is adjusted to a desired flow rate by a mass flow controller, and then connected to the nozzle. 114 to the decomposition space (odor).

115 is a microwave waveguide into which microwaves are introduced from a microwave oscillator (not shown).

116-1. 116-2 is a magnet that serves to draw plasma generated by microwaves into the decomposition space (C5), and generates active species such as H* in the plasma chamber 117. Also, 117 is a microwave soflexor. Prevents microwaves from leaking into the film forming space (4).The active species is
It is sufficiently spread and made uniform in the plasma chamber 117. Furthermore, it reacts with the precursor of the raw material gas discharged from the multi-nozzle 111 in the meeting part (2), and a desired deposited film is formed on the substrate 103 in the film-forming space (4).

The multi-nozzle 111 for introducing the precursor is shown in FIG.
) using a ring-shaped object as shown.

It may be possible to introduce the precursor toward the center, or as shown in Fig. 1 (
A method of introducing from the center toward the outer periphery as shown in C) may also be used.

In this example, a ring-shaped multi-nozzle is used, and an inlet is provided slightly toward the base from the center.
The cross section of the inlet used was one in which 24 circular holes of 0.5 wφ were arranged.

First, Corning 7059 gas is used as the base 103, placed on the support stand 102, and an exhaust device (not shown) t-
The inside of the film forming chamber 101 was evacuated and the pressure was reduced to 10'' Torr.
A 059 glass substrate was heated to 250°C.

Therefore, 81 is supplied from a cylinder (not shown) through the supply pipe 10
308 CCM of 2F6 was introduced. At this time, the temperature of the furnace 109 was preheated to 650°C.

H2 gas 'i 808CCM from the other gas supply pipe 113
and 40 SCCM of Ar gas were introduced into the plasma chamber 117. On the other hand, the rotation speed of a mechanical booster pump (not shown) in the exhaust system 107 and the barrier 1 luorifice pulp were adjusted to 0.2 T with the Paratron vacuum gauge 118.
I made it so that it becomes orr.

Next is the microwave noyaro'! i230W was input to generate plasma in the plasma chamber 117 to form a film.

The distance between reflector 117 and multi-nozzle 111 is 10
m, and the distance between the multi-nozzle 111 and the base 103 is 2
@ The a-3i :H(:F) film obtained by the above method was 200.
■Film thickness distribution within φ is ±8% or less, dark conductivity (σ, ).

ημτ, activation energy, optical bandgap (E
gopt ) and other characteristics are ±5 at any position on the substrate.
The variation was suppressed to within %.

Example 2 In FIG. 1, the distance between the multi-nozzle 111 and the base 103 is 80 cm, and the H2 gas flow rate is t-1508 CCM.
, Ar gas flow rate -i 50 SCCM and film forming chamber 1
The film was formed by applying a microwave power of t-280 W at a pressure of 1 & 0.05 Torr.

The Si film obtained by the above method had a poor film thickness distribution of ±25% and was thin in the center, but the diameter of the ring-shaped po + JSi film obtained was about 1 point as a result of TEM observation. .

Example 3 In FIG. 1, a multi-nozzle 111t for introducing raw material gas and/or precursor is used - a type of multi-nozzle that ejects from the center toward the treatment as shown in FIG. 1(c),
Film formation was performed under the same conditions as in Example 2.

The multi-nozzle 111 used had 24 holes of 0.5 φ in two rows.

The S1 film obtained by the above method had a uniform poly S1 over 120 .phi. Note that when an s1 wafer was used as the base 103, epitaxial growth was performed.

After forming a film under the above conditions using a 111-sided St wafer, R
It was confirmed by HIED that it was epitaxial.

Example 4 In Figure 1, the 5t2r6 gas flow rate is 30 SCCM.

G・2'6 Gas flow rate 'i 38 CCM was simultaneously supplied from the raw material gas supply pipe 10g, and other conditions were the same as in Example 1.
A 81:G.:H (:F) film was formed.

The film obtained by the above method has an Egop within the range of 200 wφ.
A film with a narrow optical breadth gap f@ of t=1.34 eV C±1.4%) was obtained.

Example 5 In FIG. 1, Corning 7059,
A solar cell having a configuration as shown in FIG. 4 was fabricated using the f-lass substrate on which 100 ml of TCO was vapor-deposited using the following procedure.

812F6FF (not shown) 208CCM 5IF4 diluted to 0.5 PF5 with 20S
CCM is supplied from the original 'Prf supply pipe 108, and 650
After being heated and excited in a furnace 109 heated to .degree. C., it was introduced into the meeting space (2) through a multi-nozzle 111. On the other hand, H2 gas 1
208CCM and Ar gas 40SCCM? Gas supply pipe 1
13 to Glazma Exhibition 117.

Next, the pressure inside the film forming chamber 101 was adjusted to 0.3 Torr, and a microwave power generator T-260W was applied to reduce the TCO.
Approximately 1001 n-type A-8T is deposited on the substrate 103 on which
:H (:F) conversion film was formed. (This a-81:H(:
F) The film contains a microcrystalline layer) Furthermore, intrinsic a-8l:H (:
F) Approximately 50,001 films were formed.

Next, the gas flow rate of 5i2p'6 is 20 SCCM, and 5i
BF, Goss t' 208 diluted to 0.4% with p4
CCM is supplied from the raw material gas supply pipe 108, and the others are n-type a
-8i:H (:F) film under the same conditions as the p-type a-8
Approximately 1501 t of 1:H (:F) membranes were stacked.

Next, about 10,001 t of AA electrodes were laminated by evaporation method and then modularized to fabricate 49 25.4 x 25.4 square solar cell solar modules at once.

This element is referred to as t-(a).

In addition, in order to fabricate solar cells with different configurations, TCOt
- n-type a-at:I'! on the deposited substrate 103 in a similar manner to the above method; (:F) membrane t-100X, a-8IG @:H (:F) membrane @3000X, Pf under the conditions of Example 4
fia-81:H(:F) film 1&:1O01, n-type a-
8t:H(:F) film t-1001, and a-8l:H(:F) film '13000 on top of it under the same conditions as Example 1.
1. P-type a-8l:H (:F) films were stacked 100 times.

Next, there are about 1000 Ani electrodes! By vapor deposition and modularization, a solar cell solar module with a tandem structure of 25.4 x 25.4 cm was fabricated. This element is referred to as t-(b).

Further, as a reference example, it was fabricated by glow discharge method (GD) using 5ta4 and 5ir46 on a TCO vapor-deposited glass substrate. A solar cell with a pln configuration was created. This element is designated as (C).

Table 1 shows the evaluation results of the above solar cell elements.

The average value of conversion efficiency is the average of 49 submodules that can be made from one board, but using this example, it was found that the variation was less than ±5 inches for both nine elements (a) and (b). It was done.

Table 1 Example 6 As another method for introducing active species into the film forming space over a wide area, an example using a heating element made of a transition metal is shown in FIG.

In FIG. 2, 201 is a film forming chamber, and the method of installing the substrate '203, the exhaust system 207, and the method of supplying raw material gas are the same as in FIG.

Reference numeral 219 is a heating element made of a transition metal, and has a structure that allows it to be heated by being supplied with electric power from the outside. Supplied from the active species generation gas supply pipe 213 and the nozzle 214
The activated species generating gas introduced from the heating element 219 is decomposed or activated on or near the heated heating element 219 to generate active species. Furthermore, a deposited film is formed on the substrate 203 by reacting with the aforementioned precursor in the association space (2).

In this example, all 0.5-φ W filaments were used in the heating element 219, and when 120 W of power was supplied from the outside, the introduced hydrogen gas (H2) passed through the heating element 219'i made of W filaments. When this occurs, it is activated by the catalytic action and becomes activated hydrogen, etc., and it is confirmed that a large amount of activated hydrogen evenly reaches the substrate 206.
Due to the color change of w03, it was decided that it was in trouble.

The substrate 203'i is placed on the support table 202, and the inside of the film forming chamber 20'1 is evacuated using an exhaust device (not shown) t-25.
It was heated to 0° C. and then the pressure was reduced to 10 Torr.

Therefore, 812F6 gas is supplied from an inlet (not shown) to the supply pipe 20.
8 to 10,800M was supplied and introduced from the multi-nozzle 211. At that time, the temperature of the furnace 209 was preheated to 650°C.

From the other gas supply pipe 213, H2 gas 'i 20800M
Introduced into the activation chamber 220 from the nozzle 214, and the reaction chamber 20
The pressure inside No. 1 was set at 0.5 Torr. Furthermore, power 't-120W is supplied to KW filament 219, and approximately 1700
WX was carried out by heating to ℃. At that time, the distance between the filament and the substrate was set to 200 square meters. The multi-nozzle 111 used had 24 holes of 0.5 φ in two rows.

The a-SiH:P film obtained by the above method has a diameter of 200 mφ.
Variations in film thickness distribution and properties such as Ea a Ig'P' were within ±8%.

Example 7 The W filament 109 in FIG. 2 was replaced with a W mesh 219' as shown in FIG. 2(c).

Furthermore, S1□F6 is a gas flow 'ft-5SCCM, H2 is a gas flow of 50SCCM, and the pressure inside the reaction chamber is Q, 5 Torr.
The film was otherwise formed in the same manner as in Example 6.

The deposited film obtained by the above method is a polycrystalline Si film, and the dale size is approximately 750 to 90 mm over the entire area within 2001φ.
It was 00X.

Approximately 1000 pieces of poly S1 were each deposited on separate Corning 7059 glass substrates in a manner similar to Example 3 and Example 7.
A thin film was deposited. As a comparative example, 11,000 thick poly S1 thin films were deposited on a quartz substrate by the glow discharge CD method at a substrate temperature of 600° C. (deletion size was about 500×).

Based on these substrates, a-81, N4 film (f-) insulating film (
A coplanar type TF'r having a diameter of about 3000×)t" was prepared (L=1000.m, W=101trn). Thereafter, heat treatment was performed at 200° C. for 1 hour in an N2 atmosphere.

1! Table J2 shows the characteristics of the above three types of TFTs. Example 7
TF'T was found to have the widest range and stable characteristics.

〔Effect of the invention〕

According to the deposited film forming method of the present invention, it is easy to uniformly deposit Ixt with good quality over a large area, and it is possible to form a deposited film with good reproducibility and high efficiency.

Further, a polysilicon deposited film can be obtained at a low substrate temperature of 250° C. or less, and it is possible to easily manage the film formation conditions and make the film more valuable.

[Brief explanation of drawings]

FIG. 1 is a schematic diagram for explaining the configuration of a deposited film forming apparatus for carrying out the present invention. FIG. 2 is a schematic diagram for explaining the configuration of a deposited film forming apparatus using a transition metal heating element according to another embodiment. FIG. 3 is a schematic diagram for explaining the configuration of a deposited film forming apparatus using a conventional dish method. FIG. 4 is a schematic cross-sectional view for explaining the structure of a PIN type photoelectric conversion element that can be manufactured by the method of the present invention. 101.201... Film forming chamber, 102.202... Substrate support, 103, 203-... Substrate, 104, 2
04... Heater for heating the substrate, 105, 205-...
・Conductor wire, 106.206...Thermocouple, 107.207
...exhaust system, 108.208...raw material gas supply pipe,
109゜209...Infrared image furnace, 110, 2
10--Precursor transport pipe, 111, 211--Multi nozzle, 112.212--Heater, 113.21
3... Supply pipe for active earth-covering gas, etc., 114, 21
4--Introduction nozzle for active species generation gas, etc., 115,2
15...Microwave waveguide, 116-1.116-2
...Magnet), 117...Plasma chamber, 118-
・・Gas pressure monitor (Beratron vacuum gauge), 219-・・
tungsten filament), 220...activation chamber,
(4)... Film formation space - (B)... Decomposition space, (Q.
...Activation space (decomposition space), (2)... Meeting area (meeting space). Agent Patent Attorney Minoru Yamashita Child Figure 1 (G) Figure 1 (b) ↑ ↑ Figure 2 (a) Figure 2 (b) Figure 2 (c) Figure 3 Figure 4

Claims (1)

[Claims] In the film formation space (A) for forming the deposited film on the substrate, a precursor that is a raw material for forming the deposited film is generated in the activation space (B), and in the activation space (C). In a method for forming a deposited film, the deposited film is formed on the substrate by introducing an active species that is generated by the method and interacts with the precursor.
Two or more introductions in which the active species are introduced into the film forming space (A) through an introduction port with a wide cross section, and the precursors are distributed in an introduction pipe arranged near the introduction port of the active species. A deposited film forming method characterized by forming a deposited film by introducing it through the mouth.