JPH0645889B2 - Deposited film formation method - Google Patents

Description

The present invention relates to a functional film, in particular, an electronic device such as a semiconductor device, a photosensitive device for electrophotography, an optical input sensor device for an optical image input device, and the like. The present invention relates to a method for forming a functional deposited film useful for an application.

[Conventional technology]

Conventionally, an amorphous or polycrystalline functional thin film such as a semiconductor film, an insulating film, a photoconductive film, a magnetic film, or a metal film is individually formed from the viewpoint of desired physical characteristics or application. The method has been adopted.

In order to form a deposited film, a vacuum vapor deposition method, a plasma CVD method, a thermal CVD method, a photo CVD method, a reactive sputtering method, an ion plating method and the like have been tried, and generally,
The plasma CVD method is widely used and commercialized.

However, since the deposited film obtained by these methods for forming a deposited film is required to be applied to electronic devices and optoelectronic devices that are required to have higher functions, electrical and optical characteristics and repeated use There is room to improve the overall characteristics in terms of fatigue characteristics, usage environment characteristics, and productivity and mass productivity including uniformity and reproducibility.

A reaction process in forming a deposited film by a plasma CVD method which has been generalized in the past is a so-called conventional thermal process.
Compared with the VD method, it was considerably complicated, and its reaction mechanism was not clear. In addition, there are many formation parameters of the deposited film (eg, substrate temperature, flow rate and ratio of introduced gas, formation pressure, high frequency power, electrode structure, reactor structure, exhaust rate, plasma generation method, etc.). Due to the combination of many parameters, the plasma was sometimes in an unstable state and had a considerable adverse effect on the formed deposited film. In addition, it is difficult to generalize the manufacturing conditions because it is necessary to select a device-specific parameter for each device.

Among them, for example, in the case of an amorphous silicon film, it is currently best to form the amorphous silicon film by the plasma CVD method from the viewpoint that, for example, the one having electrical and optical characteristics that can sufficiently satisfy each application can be developed. Has been done.

However, depending on the application of the deposited film, it may be necessary to sufficiently satisfy the large area, the uniformity of the film thickness, and the uniformity of the film quality to achieve reproducible mass production.
In forming a deposited film by the method, a large amount of capital investment is required for mass production equipment, the management items for mass production are complicated, the management allowance is narrow, and the adjustment of equipment is delicate, These are pointed out as problems to be improved in the future.

On the other hand, in the conventional technique by the ordinary CVD method, a high temperature is required, and a deposited film having satisfactory characteristics on a company level has not been obtained.

These problems remain as a larger problem especially when forming an insulating film of a compound containing Al, C, B or Zr.

As described above, in forming a functional film, it is earnestly desired to develop a method for forming a deposited film, which can ensure practical properties and can be mass-produced by a low-cost apparatus while maintaining uniformity.

〔Purpose〕

An object of the present invention is to eliminate the above-mentioned drawbacks of the deposited film forming method, and at the same time provide a novel deposited film forming method which does not depend on the conventional forming method.

Another object of the present invention is to provide a deposited film forming method which can save energy and can easily control the film quality and can obtain a deposited film having uniform characteristics over a large area.

Still another object of the present invention is to provide a deposited film forming method which is excellent in productivity and mass productivity, and which can easily obtain a film having high quality and excellent physical properties such as electrical, optical and semiconductor properties. is there.

[Means for solving problems]

The deposited film forming method of the present invention which achieves the above-mentioned object, comprises a starting material containing Al, C, B or Zr which can be made into a gaseous state for forming a propulsion film, and a gaseous halogen having a property of oxidizing the starting material. A precursor in an excited state is chemically generated by introducing a system oxidant into the reaction space and bringing them into contact with each other, and the precursor is used as a supply source of deposited film constituents on the substrate in the film formation space. It is characterized in that an insulating film is formed.

[Action]

According to the above-described deposited film forming method of the present invention, energy saving as well as large area, film thickness uniformity, and film quality uniformity are sufficiently satisfied to simplify management and mass production, and to be used in a mass production apparatus. It does not require a large capital investment, the management items for its mass production are clarified, the management allowance range is wide, and the adjustment of the device is easy.

In the deposited film forming method of the present invention, the raw material containing Al, C, B or Zr which can be made into a gas for forming the deposited film is oxidized by contact with a gaseous halogen-based oxidizing agent. The type and characteristics of the target deposited film,
It is appropriately selected according to the intended use and the like. In the present invention, the above-mentioned gaseous raw material and gaseous halogen-based oxidant may be those that are gaseous when introduced and contacted, and in the normal case, even a gas may be used. It can be liquid or solid.

When the raw material for forming the deposited film or the halogen-based oxidant is a liquid or a solid, a carrier gas such as Ar, He, N ₂ or H ₂ is used, and bubbling is performed while adding heat as necessary. As a result, the raw material for forming the deposited film and the halogen-based oxidizing agent are introduced into the reaction space in a gaseous state.

At this time, the partial pressure and mixing ratio of the gaseous raw material and the gaseous halogen-based oxidant are adjusted by adjusting the flow rate of the carrier gas or the vapor pressure of the raw material for forming the deposited film and the gaseous halogen-based oxidant. Is set.

Examples of the raw material for forming a deposited film used in the present invention include, for example, an organometallic compound containing Al, C, B or Zr, a hydride or a halogen if a deposited film having good electrical insulation is obtained. Compounds can be mentioned.

Specifically, as the compound containing Al, Al (CH ₃ )
₃ , Al (CH ₃ ) ₂ Cl, Al (CH ₃ ) Cl ₂ , A
l ₂ (CH ₃ ) ₂ Cl ₃ , Al (C ₂ H ₅ ) ₃ , Al
_{(C 3 H 7) 3,} Al (i-C 3 H 7) 3, Al (i-
_{C 4 H 9) 3, Al} (OCH 3) 3, Al (OC
₂ H ₅ ) ₃ , Al (OC ₄ H ₉ ) ₃ , AlCl ₃ , Al
Examples of the compound containing Br ₃ , AlI ₃ and C include CH ₄ ,
_{C 2 H 6, C 3 H} 8, C 4 H 10, C 2 H 4, C 3 H 6,
Examples of the compound containing C ₄ H ₈ , C ₂ H ₂ , C ₃ H ₄ and B include B (CH ₃ ) ₃ , B (C ₂ H ₅ ) ₃ and B (C
₃ H ₇ ) ₃ , B (C ₄ H ₉ ) ₃ , B (OCH ₃ ) ₃ , B
_{(OC 2 H 5) 3,} B (i-OC 3 H 7) 3, B (O-
_{C 4 H 9) 3, B} 2 H 6, BCl 3, BBr 3, B
Examples of the compound containing I ₃ and Zr include Zr (CH ₃ ) ₄ and Z
r (C ₂ H ₅ ) ₄ , Zr (C ₃ H ₇ ) ₄ , Zr (C ₄ H
₉ ) ₄ , Zr (OCH ₃ ) ₄ , Zr (OC ₂ H ₅ ) ₄ ,
Zr (OC ₃ H ₇ ) ₄ , Zr (OC ₄ H ₉ ) ₄ , Zr
_{(CH 3) 2 (C 5} H 5) 2, ZrCl 2 (C 5 H 5)
_{2 and the} like.

Of course, these raw material substances may be used alone or in combination of two or more.

The halogen-based oxidant used in the present invention is made gaseous when introduced into the reaction space, and at the same time, it only contacts the gaseous raw material for forming a deposited film which is introduced into the reaction space. It has the property of effectively oxidizing,
_{F 2, Cl 2, Br 2} , I 2, halogen gas such as ClF, fluorine nascent state, chlorine, can be bromine and so mentioned as valid.

These halogen-based oxidants are gaseous, and are introduced into the reaction space at a desired flow rate and supply pressure together with the gas of the raw material for forming the deposited film, and are mixed and collided with the raw material. By efficiently oxidizing the raw material, a plurality of kinds of precursors including a precursor in an excited state are efficiently generated. The excited state precursors and other precursors that are produced serve as a source of constituents of the deposited film, at least one of which is formed.

The generated precursor decomposes or reacts to become a precursor in another excited state or a precursor in another excited state, or releases energy as necessary but forms a film as it is. By touching the surface of the substrate disposed in the space, a deposited film having a three-dimensional network structure is formed when the substrate surface temperature is relatively low, or a crystalline deposited film is formed when the substrate surface temperature is high.

In the present invention, the deposited film forming process proceeds smoothly, and a film having high quality and desired physical properties can be formed. A combination, a mixing ratio of these, a pressure at the time of mixing, a flow rate, a film forming space internal pressure, a gas flow rate, and a film forming temperature (a substrate temperature and an atmospheric temperature) are appropriately selected as desired. These film forming factors are organically related, and are not determined individually but are determined according to each other under mutual relation. In the present invention, the ratio of the amounts of the gaseous raw material substance for forming a deposited film and the gaseous halogen-based oxidant introduced into the reaction space is related to the film forming factors related to the above film forming factors. In this case, the introduction flow rate ratio is preferably from 1/20 to 100/1, more preferably from 1/5 to 50/1, although it can be determined as desired.

The pressure at the time of mixing when introduced into the reaction space is preferably higher in order to stochastically enhance the contact between the gaseous raw material and the gaseous halogen-based oxidant, but the reactivity is taken into consideration. Then, it is preferable to appropriately determine the optimum value as desired. The pressure at the time of mixing is determined as described above, but the pressure at the time of introducing each is preferably 1 × 10 6.
^-7 atm to 5 atm, more preferably 1 x 10 ^-6 atm to 2 atm.

The pressure in the film-forming space, that is, the pressure in the space where the substrate on which the film is to be formed is disposed, is the precursor (E) in the excited state generated in the reaction space and the precursor in some cases. The precursor (D) derived from the body (E) is appropriately set as desired so as to effectively contribute to film formation.

The internal pressure of the film formation space is the pressure introduced into the reaction space between the base material for forming a deposited film and the gaseous halogen-based oxidant when the film formation space is open and continuous with the reaction space. In relation to the flow rate and the flow rate, it is possible to make adjustments by adding, for example, differential exhaust or using a large exhaust device.

Alternatively, when the conductance of the connecting portion between the reaction space and the film formation space is small, an appropriate exhaust device is provided in the film formation space,
The pressure in the film forming space can be adjusted by controlling the exhaust amount of the apparatus.

Further, when the reaction space and the film formation space are integrated and the reaction position and the film formation position are spatially different from each other, differential evacuation as described above or a large size with sufficient evacuation capacity is performed. It suffices if an exhaust device is provided.

As described above, the pressure in the film forming space is determined by the relationship between the gaseous source material introduced into the reaction space and the introduction pressure of the gaseous halogen oxidant, and preferably 0.001 T
orr to 100 Torr, more preferably 0.01 Torr
-30 Torr, optimally 0.05-10 Torr is desirable.

Regarding the gas flow type, when the raw material for forming the deposited film and the halogen-based oxidant are introduced into the reaction space, these are uniformly and efficiently mixed, and the precursor (E) is efficiently mixed. It is necessary to design in consideration of the geometrical arrangement of the gas inlet, the substrate and the gas outlet so that the film can be properly formed and the film can be properly formed. One suitable example of this geometric arrangement is shown in FIG.

The substrate temperature (Ts) at the time of film formation is individually set as desired according to the gas species used, the number of species of the deposited film to be formed and the required characteristics. In order to obtain, it is preferable that the temperature is from room temperature to 450 ° C, more preferably 50 to 400 ° C. In particular, when forming a crystalline deposited film having better electric insulation, the substrate temperature (Ts) is preferably 300 to 600 ° C.

As the ambient temperature (Tat) of the film formation space, the generated precursor (E) and the precursor (D) do not change into chemical species unsuitable for film formation, and the precursor (E) is efficiently generated. ) Is appropriately determined as desired in relation to the substrate temperature (Ts).

The substrate used in the present invention may be either conductive or electrically insulating as long as it is appropriately selected according to the intended use of the deposited film to be formed. As the conductive substrate, for example, NiCr, stainless steel, Al, C
r, Mo, Au, Ir, Nb, Ta, V, Ti, Pt,
Examples include metals such as Pd and alloys thereof.

As the electrically insulating substrate, a film or sheet of synthetic resin such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene and polyamide, glass, ceramics, paper and the like are usually used. It is preferable that at least one surface of these electrically insulating substrates is subjected to a conductive treatment, and another layer is provided on the surface subjected to the conductive treatment.

For example, in the case of glass, the surface is NiCr, Al, C
r, Mo, Au, Ir, Nb, Ta, V, Ti, Pt,
Pd, In ₂ O ₃ , SnO ₂ , ITO (In ₂ O ₃ + S
nO ₂ ), a conductive film is provided by a thin film, or a synthetic resin film such as a polyester film is NiCr, Al, Ag, Pb, Zn, Ni, Au,
The surface is subjected to a conductive treatment by treatment with a metal such as Cr, Mo, Ir, Nb, Ta, V, Ti, Pt by vacuum vapor deposition, electron beam vapor deposition, sputtering, or the like, or by laminating with the metal. The shape of the support may be any shape such as a cylindrical shape, a belt shape and a plate shape, and the shape is determined as desired.

The substrate is preferably selected from the above in consideration of the adhesion and reactivity between the substrate and the film. Furthermore, if the difference in thermal expansion between the two is large, a large amount of strain may occur in the film, and a good quality film may not be obtained. Therefore, select and use a substrate with a close difference in thermal expansion between the two. Is preferred.

Further, since the surface condition of the substrate is directly related to the structure (orientation) of the film and the generation of the conical structure, it is necessary to treat the surface of the substrate so that the film structure and the film structure can obtain desired characteristics. Is desirable.

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

The deposited 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.

A reaction space and a film formation space are provided in the apparatus body.

101 to 105 are cylinders filled with gas used for film formation, 101a to 105a are gas supply pipes, 101b to 105b are mass flow controllers for adjusting the flow rate of gas from each cylinder, 101
c-105c are gas pressure gauges, 101d-105, respectively.
d and 101e to 105e are valves and 101, respectively.
Reference numerals f to 105f are pressure gauges indicating the pressures in the corresponding gas cylinders.

Reference numeral 106 denotes a container for containing a liquid or solid raw material, which has a heating device (not shown) used as necessary, 106a,
106b is a gas supply pipe, and 106c is a valve.

Reference numeral 120 denotes a vacuum chamber having a structure in which a gas introducing pipe is provided in an upper portion thereof, and a reaction space is formed in the downstream of the pipe, and the substrate 1 faces the gas outlet of the pipe.
It has a structure in which a film formation space in which the basic holder 112 is provided so that 18 is arranged is formed. The pipes for introducing gas have a triple concentric arrangement structure, and the gas from the gas cylinder 101 and the gas from the gas cylinder 102 into which the raw material from 106 is introduced are introduced. It has the 2nd gas introduction pipe 110 and the 3rd gas introduction pipe 111 into which gas from gas cylinders 103-105 is introduced.

For the gas discharge to the reaction space of each gas introduction pipe, it is designed such that the inner pipe is located farther from the surface position of the substrate. That is, the respective gas introduction pipes are arranged so that the outer pipes surround the inner pipes.

The supply of gas from the pipe cylinders to the respective introduction pipes is performed by gas supply pipelines 123 to 125, respectively.

The gas introduction pipes, the gas supply pipelines, and the vacuum chamber 120 are vacuum-exhausted by a vacuum exhaust device (not shown) via the main vacuum valve 119.

The substrate 118 is installed 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 present invention, the distance between the substrate and the gas outlet of the gas introduction pipe is in an appropriate state in consideration of the type of the deposited film to be formed, its desired characteristics, the gas flow rate, the internal pressure of the vacuum chamber, etc. However, it is preferably several mm
It is desirable that the length is 20 cm, more preferably 5 mm to 15 cm.

Reference numeral 113 is a heater for heating the substrate, which heats the substrate 118 to an appropriate temperature during film formation, preheats the substrate 118 before film formation, and further heats the film after film formation to anneal the film. Is.

The substrate heating heater 113 is connected to the power source 1 through the lead wire 114.
Power is supplied by 15.

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

Hereinafter, the present invention will be specifically described with reference to Examples.

Example 1 Using the film forming apparatus shown in FIG. 1, a deposited film is prepared by the method of the present invention as follows.

He gas filling the cylinder 101 at a flow rate of 10 sc
Al (C H ₃ ) ₃ was bubbled into the raw material container 106 containing the gas and bubbled through the gas introduction pipe 109 together with He gas at about 0.001 mol / min to vaporize Al (C
H ₃ ) ₃ is the F ₂ charged in the cylinder 103 with NO gas filling the cylinder 102 at a flow rate of 5 sccm.
A He gas with a gas flow rate of 10 sccm and a cylinder 104 was introduced at a flow rate of 10 sccm through the gas introduction pipe 111 into the vacuum chamber 102.

At this time, the pressure inside the vacuum chamber 120 was adjusted to 0.6 Torr by adjusting the opening / closing degree of the vacuum valve 119. The distance between the gas inlet 111 and the substrate was set to 3 cm by using quartz glass (15 cm × 15 cm) in which molybdenum was vapor-deposited in advance on the substrate.

Luminous emission of reddish purple was observed at a mixed region of Al (CH ₃ ) ₃ gas, NO gas and F ₂ gas, and at 600 ° C. The substrate temperature (Ts) was set to 300 ° C.

When the gas is flowed for 3 hours in this state, the film thickness A as shown in Table 1 is obtained.
An l: O: F film was deposited on the substrate.

The unevenness of the film thickness distribution was within ± 5%.

The formed Al: O: F film has a substrate temperature of 300 ° C. and 60 ° C.
It was confirmed to be amorphous and crystalline by electron diffraction at 0 ° C.

Several 1 mmφ Al electrodes were vapor-deposited on the surface of each sample, and the specific resistance with the molybdenum electrode vapor-deposited on the quartz glass was measured. The film formation and results are shown in Example 1 in Table 1.

Examples 2 to 5 In the device used in Example 1, Al (CH ₃ ) ₂ and N were used.
O Instead of CH ₄ in the raw material gas C: F _{film, B} 2 H
₆ and NH ₃ as raw material gases, and the B: N: F film was replaced with Al (C
H ₃ ) ₃ and NH ₃ are used as source gases and an Al: N: F film is
Using r (OC ₃ H ₇ ) ₄ and CH ₄ as source gases, Zr:
The results of forming the C: F film are shown in Tables 1 and 2.

[Effect] From the above detailed description and each example, according to the deposited film forming method of the present invention, it is possible to achieve energy saving and at the same time easily control the film quality and to obtain a deposited film having uniform physical properties over a large area. can get. In addition, it has excellent productivity and mass productivity, high quality and electrical,
An insulating film with excellent characteristics can be easily obtained.

[Brief description of drawings]

FIG. 1 is a schematic diagram of a film forming apparatus used in an example of the present invention. 101-105 ... Gas cylinder, 101a-106a, 106b ... Gas introduction pipe, 101b-106b, 106b ... Mass flow meter, 101c-105c ... Gas pressure gauge, 101d-105d and 101e-105e, 106c .... Valves, 101f to 108f ... Pressure gauges, 109, 110, 111 ... Gas introduction pipes, 112 ... Substrate holders, 113 ... Substrate heating heaters, 116 ... Substrate temperature monitoring thermocouples, 118 ... Substrate, 119 ... Vacuum exhaust valve, 128 ... Heater for vaporizing raw material, 129 ... Heater for preventing raw material accumulation, respectively.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display location H01L 31/04

Claims (11)

[Claims] 1. Al, C, which can be made into a gaseous state for forming a deposited film,
A plurality of precursors containing a precursor in an excited state by introducing into the reaction space and contacting a raw material containing B or Zr and a gaseous halogen-based oxidizing agent having a property of oxidizing the raw material. Deposition characterized in that a body is chemically produced and at least one of these precursors is used as a source of deposited film components to form an electrically insulating film on a substrate in the deposition space. Film formation method. 2. Al, C, B or Zr which can be made gaseous.
The deposited film forming method according to claim 1, wherein the raw material containing is an organometallic compound. 3. Al, C, B or Zr which can be made gaseous.
The method for forming a deposited film according to claim 1, wherein the source material containing is hydride. 4. Al, C, B or Zr which can be made gaseous.
The deposited film forming method according to claim 1, wherein the source material containing is a halide. 5. The deposited film forming method according to claim 1, wherein the gaseous halogen-based oxidizing agent contains a halogen gas. 6. The deposited film forming method according to claim 1, wherein the gaseous halogen-based oxidizing agent contains a fluorine gas. 7. The deposited film forming method according to claim 1, wherein the gaseous halogen-based oxidizing agent contains chlorine gas. 8. The deposited film forming method according to claim 1, wherein the gaseous halogen-based oxidizing agent is a gas containing a fluorine atom as a constituent component. 9. The deposited film forming method according to claim 1, wherein the gaseous halogen-based oxidizing agent contains halogen in a nascent state. 10. The method according to claim 1, wherein the substrate is arranged at a position opposed to a direction in which the gaseous source material and the gaseous halogen-based oxidizing agent are introduced into the reaction space. Method for forming deposited film. 11. The deposited film forming method according to claim 1, wherein the gaseous raw material and the gaseous halogen-based oxidant are introduced into the reaction space through a transport pipe having a multi-tubular structure.