PROCESS FOR FORMING DEPOSITED FILM

Abstract: A process for forming a deposited film comprises the steps of: (a) arranging previously a substrate for formation of a deposited film in a film forming space; (b) forming a deposited film on said substrate by introducing an activated species (A) formed by decomposition of a compound (SX) containing silicon and a halogen and an activated species (B) formed from a chemical substance (B) for film formation which is chemically mutually reactive with said activated species (A) separately from each other into said film forming space to effect chemical reaction therebetween; and (c) exposing the deposited film growth surface to a gaseous substance (E) having etching action on the deposited film to be formed during the film forming step (b) to apply etching action on the deposited film growth surface, thereby effecting preferentially crystal growth in a specific face direction.

Description: BACKGROUND OF THE INVENTION Field of the Invention This invention relates to a process for forming a functional deposited film containing silicon, particularly a deposited film of polycrystalline silicon to be used for semiconductor devices, photosensitive devices for electrophotography, line sensors for image input, image pickup devices, etc. Related Background Art For example, for formation of polycrystalline silicon films, the normal pressure CVD method, the LPCVD method, the plasma CVD method, etc., have been primarily used, and, in general, the LPCVD method has been widely been used and industrialized. However, in the method of the prior art, for example, in the LPCVD method, the substrate temperature is high and glass substrated, etc., which are cheap cannot be used, and deposited film having practically useful characteristics cannot be obtained at low temperature. Also, in the plasma CVD method, while there is the advantage of making the substrate temperature lower the LPCVD method, its reaction process is complicated, and not a few ambiguities existed in its reaction mechanism. Also, there are involved a large number of parameters for formation of its deposited film (e.g. substrate temperature, flow rates and their ratios of gases introduced, pressure during film formation, high frequency power, electrode structure, structure of reaction vessel, evacuation speed, plasma generation system, etc.), and the plasma formed by combination of such a large number of parameters may sometimes became unstable to give frequently markedly bad influences to the deposited film formed. Besides, in the plasma CVD method, it is difficult to avoid damages by collision of ions or electrons against the film which is an obstacle against obtaining a film of good quality. As described above, in formation of a silicon film having polycrystallinity, it has been desired to develop a method for forming a polycrystalline silicon film of good quality with a large area by means of a device of low cost while maintaining its practically useful characteristics and uniformness. These are also applicable to other functional films such as silicon carbide films, silicon nitride films, silicon oxide films, etc. SUMMARY OF THE INVENTION The present invention provides an alternative to plasma CVD deposition and thus avoids those problems, already mentioned, inherent in such a technique. In accordance with the present invention there is provided a process for forming a silicon containing crystalline deposited film which process comprises the steps of: providing in a deposition chamber a substrate, a major surface of which is exposed; introducing separately into said deposition chamber previously activated chemically mutually reactive first and second species and causing these to react and deposit a silicon containing crystalline film upon said major surface of the substrate, said activated first species being formed by the decomposition of a compound containing both silicon and a halogen; during the deposition of said film heating said deposited film by heating means; and exposing the deposited film growth surface to a gaseous etchant to effect crystal growth in a preferential face direction, whilst increasing etchant activity by irradiating this gaseous etchant with photo-energy. The process just described can be applied to the growth of large area films. By means of this process improvements can be accomplished in productivity and in bulk production. It is also possible to achieve improvement in film forming speed, in reproducibility, in electrical and physical film characteristics and in the uniformity of film quality. By way of reference, mention is made of German Patent Application DE-3 429 899. This document discloses a process for producing a film of amorphous silicon material. In common with the present process the process disclosed includes the steps of (a) arranging a substrate in a film forming space (deposition chamber); (b) introducing into the film forming space an activated species formed from a compound containing silicon and a halogen in a preceding reaction chamber; and introducing into the film forming space an activated species from another reaction chamber, this reacting with the activated species first mentioned to deposit the film. This cited document neither concerns the deposition of crystalline film, nor does it disclose the use of any etchant species. With reference to European Patent Applications available as prior art under Art. 54(3) EPC, mention is made of the following: EP-A-0241311 concerns the growth of crystalline film in circumstances where the substrate surface is sub-divided or otherwise treated to support initial growth or nucleation at a number of spaced apart locations. EP-A-0242182 concerns the growth of a crystalline film upon a substrate the surface of which is crystalline and such therefore as to determine the orientation of material deposited upon it. This process is not limited to one in which gaseous etching is photo-assisted. EP-A-0243074 also concerns a process in which the etchant activity is photo-assisted. Growth and/or nucleation however is initiated at spaced apart locations and film is formed by laterally extended growth. EP-A-0242207 concerns a process in which the substrate surface is selectively treated by irradiation as a means of defining localised sites for initiating growth or nucleation. BRIEF DESCRIPTION OF THE DRAWINGS In the accompanying drawings: Fig. 1 is a sectional view of the main part of an example of a film forming device for embodying the process for forming a deposited film of the present invention. Fig. 2 is a schematic sectional view of the substrate having a deposited film formed according to the process of the present invention. Fig. 3 is a schematic constitutional view of the thin film transistor formed utilizing a deposited film formed according to the process of the present invention. Fig. 4 is a schematic illustration showing the main part of another example of a device for forming a deposited film for embodying the process for forming a deposited film of the present invention is applicable. Fig. 5 is a schematic illustration of another deposited film prepared according to the present invention. Fig. 6 is a schematic illustration of the main part of still another example of a film forming device for embodying the process of the present invention. Fig. 7 is a schematic illustration showing the main part of an example of a device using electron beam in practicing the present invention. Fig. 8 is a schematic illustration showing the main part of an example of a device using heater in practicing the present invention. Fig. 9 is a schematic constitutional view of yet another example of a film forming device for embodying the process for forming a deposited film of the present invention. Fig. 10 is a schematic partial perspective view of the thin film transistor formed utilizing a deposited film formed according to the process of the present invention. Fig. 11 is a schematic sectional view of a substrate having a deposited film formed thereon according to the process of the present invention. Fig. 12 is a schematic illustration showing the main part of an example of a device using a laser beam in practicing the present invention. Fig. 13 is a schematic illustration showing the main part of an example of a device using a halogen lamp in combination with a Xe lamp in practicing the present invention. DESCRIPTION OF THE PREFERRED EMBODIMENTS So that this invention can be better understood, embodiments thereof will be described now and reference will be made to the drawings. The description that follows is given by way of example only. The following process for forming a deposited film, comprises a step (A) of previously providing a substrate on which a deposited film is to be formed in a film forming space; a step (B) of introducing into the film forming space an activated species (A) formed by decomposition of a compound containing silicon and a halogen and an activated species (B) formed from a chemical substance for film formation which is chemically mutually reactive with said activated species (A) separately from each other and permitting both species to react chemically with each other thereby to form a deposited film on the substrate; and a step (C) of preferentially effecting, during formation of said deposited film, crystal growth in a specific face direction by subjecting the growing surface of said deposited film to a gaseous material having etching action on said deposited film formed to thereby apply etching action on the growing surface of said deposited film. In the process described above, in place of exciting plasma in the film forming space for formation of a deposited film, chemical mutual interaction is caused to occur in the co-presence of an active species (A) formed by decomposition of a compound containing silicon and a halogen and an active species (B) formed from a chemical substance for film formation to thereby effect film formation, and therefore a deposited film of good quality can be obtained. Also, by controlling the atmosphere temperature in the film forming space and the substrate temperature freely as desired, the CVD method can be made more stable. This process differs from the CVD process of the prior art in that it uses activated species which are previously activated in a space (hereinafter referred to as the activation space) different from the film forming space. By doing so, the film forming speed can be dramatically increased, and also the substrate temperature can be lowered to a great extent. Further, in addition, by introduction of a gaseous material having etching action during the film formation step it has become possible to form a polycrystalline film having only a specific face direction namely a polycrystalline film of good quality with strong orientability and large grain size. The activated species (A) formed in the activation space (A) should preferably be selected and used as desired from those having the life of 0.1 sec. or longer, more preferably 1 sec. or longer, optimally 10 sec. or longer, from the standpoint of productivity and easiness in handling, and the constituent elements of the activated species (A) become components constituting the deposited film formed in the film forming space. Also, the chemical substance for film formation is activated by the action of an activation energy in the activation space (B) before introduction into the film forming space and introduced into the film forming space to undergo chemical mutual reaction with the activated species (A) introduced at the same time from activation spece (A) and containing constituent elements which become the constituent components of the deposited film formed. As the compound containing silicon and halogen to be introduced into the activation space (A), there may be employed, for example, chain or cyclic silane compounds of which hydrogen atoms are partially or wholly substituted with halogen atoms, typically chain silicon halides represented by Si u Y 2u+2 (u is an integer of 1 or more, Y is at least one element selected from F, Cl, Br and I) and cyclic silicon halides Si v Y 2v (v is an integer of 3 or more, and Y has the same meaning as defined above), chain or cyclic compounds represented by Si u H x Y y (u and Y have the same meanings are defined above, x + y = 2u + 2). Specific examples may include gaseous or readily gasifiable compounds such as SiF₄, (SiF₂)₅, (SiF₂)₆, (SiF₂)₄, Si₂F₆ , Si₃F₈ , SiHF₃, SiH₂F₂ , SiCl₄, (SiCl₂)₅, SiBr₄, (SiBr₂)₅, Si₂Cl₆, Si₂Br₆, SiHCl₃, SiH₃Cl, SiH₂Cl₂, SiHBr₃, SiHl₃, Si₂Cl₃F₃, and the like. For formation of the activated species (A), in addition to the above compound containing silicon and halogen, single substance of silicon, other silicon compounds, hydrogen, a halogen compound (e.g., F₂ gas, Cl₂ gas, gasified Br₂, I₂, etc.) can be used in combination, if desired. As the method for forming activated species (A) in the activation space (A), there may be employed various activation energies such as electrical energies, including microwave, RF, low frequency, DC, etc., heat energies such as heater heating, IR-ray heating, etc., photoenergy, etc. in view of respective conditions and the device. As the above chemical substance for film formation for forming activated species (B) in the activation space (B) to be used in the process of the present invention, hydrogen gas and/or a halogen gas (e.g. F₂ gas, Cl₂ gas, gasified Br₂, I₂, etc.) may be advantageously used. Also, in addition to these chemical substances for film formation, for example, an inert gas such as helium, argon, neon, etc., may be also employed. When a plural number of these chemical substances for film formation are to be employed, they can be previously mixed and then introduced under gaseous state into the activation space (B), or alternatively these chemical substances for film formation may be fed individually from the respective independent feeding sources to be introduced into the activation space, or they can be introduced into the respective independent activation spaces to be individually activated. The proportion in amount of the above activated species (A) to the activated species (B) to be introduced into the film forming space may suitably be determined depending on the film forming conditions, the kind of the activated species, etc., but may preferably be 10 : 1 to 1 : 10, (introducing flow rates ratio), more preferably 8 : 2 to 4 : 6. Also, the deposited film formed can be doped with an impurity element during or after film formation. As the impurity element to be used, there may be employed, as p-type impurity, an element belonging to the group IIIA of the periodic table such as B, Al, Ga, In, Tl, etc. and, as n-type purity, an element belonging to the group VA of the periodic table such as P, As, Sb, Bi, etc. as suitable ones. Particularly, B, Ga, P and Sb are most preferred. The amount of the impurity to be doped may be determined suitably depending on the desired electrical and optical characteristics. As the substance containing such an impurity atom as the component (substance for introduction of impurity), it is preferable to select a compound which is gaseous under normal temperature and normal pressure, or gaseous at least under the activation conditions film and can be readily gasified by a suitable gasifying device. Such compounds may include PH₃, P₂H₄, PF₃, PF₅, PCl₃, AsH₃, AsF₅, AsCl₃, SbH₃, SbF₅, SiH₃, BF₃, BCl₃, BBr₃, B₂H₆, B₄H₁₀, B₅H₉, B₅H₁₁, B₆H₁₀, B₆H₁₂, AlCl₃, etc. The compounds containing impurity element may be used either singly or as a combination of two or more compounds. The compound containing impurities as element may be directly introduced under gaseous state into the film forming space, or alternatively activated previously in the activation space (A) or the activation space (B) or a third activation space (C) before introduction into the film forming space. During the film forming step, that is (a) during film formation etching action is applied on the growth surface of the deposited film at the same time, or (b) etching action is applied on the growth surface of the deposited film with film formation intermitted, whereby crystal growth can be effected preferentially in a specific face direction to give a deposited film with good crystallinity. The etching action in the case of the above (b) may be effected within the film forming space or alternatively in an etching space separate from the film forming space. As the gaseous or readily gasifiable substance for etching (E) having etching action on the deposited film containing silicon, there may be included single substances of halogen, halide compounds or activated species (C) formed from these. These substances (E) for etching may be introduced under gaseous state into the space where etching action is applied to the deposited film, or alternatively in the case where the substance (E) is formed by the surface reaction on the surface of the deposited film of the above activated species (A) or the above activated species (B), or formed from the chemical reaction between the activated species (A) and the activated species (B), etching action is applied on the growth surface of the deposited film simultaneously with film formation. For example, as an example in which the substance for etching is formed by the above surface reaction, the reaction between an activated species of halogen and hydrogen or a halogen and activated species of hydrogen occurs on the growth surface of the deposited film, and hydrogen halide (HX) is released from the growth surface of the deposited film and the hydrogen halide becomes the substance (E) for etching. As the substance (E) having etching action in the present invention, there may be employed halogens such as F₂, Cl₂, gasified Br₂, I₂, etc., halogenated carbon such as CHF₃, CF₄, C₂F₆, CCl₄, CBrF₃, CCl₂F₂, CCl₃F, CClF₃, C₂Cl₂F₄, etc., halides including typically boron halides such as BCl₃, BF₃ and SF₆, NF₃, PF₅, etc., and further radicals such as F*, Cl*, ions such as CF₃⁺, CCl₃⁺, from these gases. These can be used also as mixtures, and the etching characteristics can be also controlled by adding O₂, H₂ and other gases in amounts which do not affect the film. As the method for etching using the above substance (E), etching and film formation may be repeated alternately by providing separately an etching space, or they can be introduced under the state having etching activity into the film forming space to effect etching action simultaneously with film formation, thereby giving the effect of limiting the growing direction of the crystalline film to accomplish the object of the present invention. During crystal growth of Si or Si containing substance, there is face direction dependence of growth speed. This may differ depending on the deposited film forming method or deposition conditions, but in the process of the present invention, it has been found that the preferential order is (110) > (111) > (100). By selecting suitably the kind of the substance (E) for etching and condition of etching under this condition, stronger orientability, namely the condition of (110) » (111) » (100) can be realized, whereby it becomes also possible to deposit a polycrystalline film with large grain size which is oriented on in the (110) face direction. Of course, it is possible to control the orientation face direction depending on the conditions. Next, the present invention is explained in more detail by referring to a typical example of a film forming device for embodying the present invention. Fig. 1 is a partial sectional view showing schematic construction of the main part of an example of the deposited film forming device for embodying the process of the present invention. In Fig. 1, 101 is a deposition chamber in which a silicon thin film is formed, and the deposition chamber 101 is internally connected to an evacuation system not shown through an evacuation outlet 106, whereby the deposition chamber 101 can be internally maintained at a desired pressure. In the deposition chamber 101, there are a set of an introducing pipe 102 for the radical containing Si and halogen which is the activated species (A) and an introducing pipe 103 for hydrogen radicals which is the activated species (B). The tips of the respective radical introducing pipes are thick at the acting chambers 108, 108A and narrowed at the outlets 109, 109A. Within the deposition chamber 101, a substrate supporting member 104 is held so as to be reciprocally movable in the direction perpendicular to the paper surface by the roller 110. And on the supporting member 104 is held a substrate 105 for deposition. The respective radicals coming out from the outlets 109, 109A are mixed and react with each other in the vicinity of the substrate within the deposition chamber 101 to form a film on the substrate. The radicals containing silicon and halogen and hydrogen radicals are formed from the respective starting material gases in the radical forming sections such as heating furnaces of plasma chambers, etc. (not shown) respectively, and thereafter introduced through the introducing pipes 102, 103, respectively into the acting chambers 108, 108A. Their amounts are controlled by massflow controllers on the gas source said from the heating furnace or plasma chamber. Roller 110 is provided for depositing a silicon thin film over the whole surface of the substrate by moving the substrate 105. The introducing pipe 111 is an introducing pipe for another gas having chemical or physical etching activity, and in some cases the gas is excited in the heating furnace or plasma furnace (not shown) and led to the outlet 114. From the outlet 114, the gas having etching activity for attacking the film is released to cut and exclude selectively bonds other than the bonds in the prescribed growth direction of the film. Introduction of the etching active gas, other than through such separate introduction pipes, can be also done through the introduction pipes 102, 103, mixed with starting gases, when the reactivity with the starting gas is low. In this process for forming a deposited film it is possible to increase the crystal grain size of polycrystal and in its turn to convert it to single crystal by irradiation of an electromagnetic wave such as light or microwave, etc., or electron beam which is a film heating means, or application of heat onto the deposited film at the early stage of the film forming step or during film formation or after film formation. When the above treatment is effected at the early stage of the film formation step it is preferred to effect it at the state of an extremely thin film of 200 nm (2000 Å ) or less, desirably 100 nm (1000 Å) or less. In this case it is desirable that film formation is once intermitted when a film of 200 nm (2000 Å) or less, desirably 100nm (1000 Å) or less has been formed, and the grain size of the crystal is enlarged or the polycrystal is converted to single crystal by irradiation of an electromagnetic wave such as light or microwave or electron beam or application of heat to prepare a base film with regular oriented faces. Then, by restarting film formation to form a deposited film with good orientation on the oriented face of the base film, it becomes possible to form a deposited film with enlarged crystal grain size or a single-crystalized deposited film over the whole film with a desired film thickness. By irradiating an electromagnetic wave or electron beam or applying heat on an extremely thin film, enlargement of grain size of crystal or single crystal formation can be effected by lower energy than in the prior art. In this case, since the amount of heat generated is small, damages given to the base substrate or diffusion of impurities can be suppressed as compared with the prior art. Also, by film formation on the extremely thin base film subjected to the above treatment, the film surface can also be made flat. Next, "during film formation" as described about refers to irradiation of an electromagnetic wave such as light or microwave or electron beam or application of heat simultaneously with film formation, and by subjecting only the surface layer of the deposited film to the above treatment, formation of a deposited film with enlarged crystal grain size or a single-crystallized deposited film rendered possible at lower energy than in the prior art. Accordingly, the amount of heat generated is small, and also the damages given to the base plate, etc., and diffusion of impurities are also small, whereby the surface can be made flat. Further, since superfluous hydrogens not contributing to the terminating of the dangling bonds in the film are withdrawn by the halogen or a compound of halogen or its activated species used in the process for forming a deposited film of the present invention, the grain size of crystal is enlarged and the dangling bonds at the crystal grain boundary are effectively terminated with atoms of halogen or hydrogen, whereby the electrical characteristic at the crystal grain boundary can be improved to result in improvement of electrical characteristic of the film as a whole. The treatment "after the deposition" as described above refers to the time point after completion of film formation, and by irradiation of an electromagnetic wave such as light or microwave or electron beam or application of heat at that point, enlargement of the grain size of crystal or single-crystallization can be effected. Further, in the present invention, the etching effect on the growth surface of the deposited film can be aided by photoenergy irradiation which gives rise to etching selectivity. That is, the substance (E) for etching is optically excited to increase etching activity, which can make crystal growth in a specific direction more efficient. This photoenergy irradiation should preferably be selected so as to act more efficiently on the substance (E) for etching than on the starting gas for film formation. Next, by referring to the drawings, an example of the method for forming a deposited film in the case of depositing a polycrystalline silicon film is described in detail. Fig. 9 is a schematic constitutional view of an example of the device for forming a deposited film for embodying the process of the present invention when photoenergy is subsidiarilly used. In Fig. 9, 901 is a deposition chamber in which formation of a deposited film such as a polycrystalline silicon film or the like is effected, and the deposition chamber 901 is internally connected to an evacuation system (not shown) through an evacuation pipe 921, whereby the deposition chamber 101 can be internally held at a desired pressure through an evacuation valve 920. The pressure in the deposition chamber 901 is controlled to 10⁻³ to 10² Pa (10⁻⁵ to 1.0 Torr), preferably 10⁻² to 10 Pa (10⁻⁴ to 0.1 Torr) In the deposition chamber 901, a desired substrate 903 is placed on the substrate supporting stand 902. 904 is a heater for heating the substrate, and electricity is supplied through a conductive wire 905 to generate heat. The substrate temperature is not particularly limited, but it should preferably be 100 to 500 °C, more preferably 150 to 400 °C, in practicing the process of the present invention. 906 through 911 are gas feeding sources, and provided corresponding to the number of silicon compounds and hydrogen, halogen compound, inert gases, compounds containing impurity elements as the component which may be optionally employed. When liquid type starting material is used, an appropriate gasifying is provided. In the drawing, the symbols of the gas feeding sources 906 through 911 affixed with a show branched pipes, those affixed with b are flow meters, those affixed with c are pressure gauges for measuring the pressures on the higher pressure side, those affixed with d or e are valves for controlling the respective gas flow rates. 912, 925, 926 are gas introducing pipes into the film forming space. 917 is a photoenergy generating device, and for example, mercury lamp, xenon lamp, carbon dioxide laser, argon ion laser, excimer laser, etc., may be employed. The light 918 directed from the photoenergy generating device 917 by use of a suitable optical system toward the whole of the substrate or a desired portion of the substrate is irradiated on the starting gas, etc., flowing in the direction of the arrowhead 919 to excite the gases, etc., of the film forming starting material and effect the reaction, thereby forming a deposited film of Si on the whole or a desired portion of the substrate 903. Also, 914 and 923 are activation spaces for forming activated species (A) and activated species (B), respectively, and 913, 922 are each microwave plasma generating device for formation of activated species. Using the device such as shown in Fig. 9, it becomes possible to preferentially effect crystal growth in a specific crystal face direction by irradiating the gaseous substance (E) having etching action or decomposed product thereof with photoenergy to thereby increase selectively the etching activity for the deposited film and also by promoting rearrangement of the lattice with a film heating means other than the means for maintaining the substrate temparature. Further, the photoenergy is imparted uniformly or selectively controllably to the gaseous substance (E) or decomposed product which have reached in the vicinity of the substrate for film formation, and use of photoenergy has conveniences such that a deposited film can be formed by irradiating the whole of a substrate by use of a suitable optical system, or that a deposited film can be formed partially only at a desired portion by selective and controlled irradiation. Also, a deposited film can be formed by irradiation of only a desired pattern portion by use of a resist, etc., and therefore it can be advantageously used. Example 1 A silicon thin film was formed on a substrate of a flat plate glass substrate (#7059), produced by Corning Co.) by means of the device shown in Fig. 1. By use of SiF₄ gas as the starting gas for formation of radicals containing silicon and halogen, this was permitted to flow into the reaction furnace maintained at 1100°C to be decomposed, followed by release through the introducing pipe 102 into the acting chamber 108. At the same time, H₂ gas was permitted to flow into the introducing pipe 103 and a microwave of 2.45 GHz was introduced at a power of 0.5W/cm² into said introducing pipe 3 to effect discharging to decompose H₂, followed by release into the acting chamber 108. The substrate temperature was maintained at 250°C The flow rate ration of the reactive starting gases at this time were changed as 10/100, 20/100, 30/100, 40/100, 50/100 of F₂ gas flow rate/SiF₄ decomposed gas (unit is SCCM), and a pressure of 67 Pa (0.5 Torr) was maintained for 1 hour for each case, whereby the films having the properties as shown in Table 1A were deposited. Of the respective samples, when drift mobility was measured for Nos. A-2, 3 and 4, it was found to be 21 for Nos. A-2, 35 for Nos. A-3 and 12 cm²/V sec for No. A-4. Thus it has been found that a very good polycrystalline film with strong orientability can be prepared. In No. A-5 with great F₂ flow rate, the film becomes amorphous. The grain size was measured according to the Debye-Scherrar method and by use of a transmission electron microscope. Example 2 By means of the same device as used in Example 1, a film was deposited on a flat plate Corning #7059 base plate as the substrate by introducing excited species of Si₂F₆ as the source into the introducing pipe 102 and introducing excited species of H₂ into the introducing pipe 103. By use of Si₂F₆ as the starting gas for formation of radicals containing silicon and halogen, this was permitted to flow into the reaction furnace maintained at 800 °C to be decomposed, followed by release from the introducing pipe 102 into the acting chamber 108. At the same time, F₂ was permitted to flow through the introducing pipe 111, and discharging was effected by introducing microwave of 2.45 GHz at a power of 0.7 W/cm², and the discharged product was released into the acting chamber 113. H₂, gas was permitted to flow through the introducing pipe 103, discharging was effected by introducing pipe 103, discharging was effected by introducing microwave of 2.45 GHz at a power of 0.5 W/cm2 to decomposed product was released into the acting chamber 108. The substrate temperature was maintained at 310 °C. At this time, the flow rate ratios of the respective starting gases were changed as 5/100, 15/100 25/100, 35/100, 50/100 of H₂ gas flow rate/Si₂F₆ decomposed gas (unit is SCCM), with H₂ being made constant 30 SCCM, and a pressure of 67 Pa (0.5 Torr) was maintained for 1 hour under the respective conditions, whereby the films having the properties as shown in Table 2A were deposited. For the respective samples Nos. A-8 and A-9, drift mobility was measured, and a high value of 40.15 cm²/V sec was obtained for each sample. Thus, it has been found that good film was deposited. Example 3 By use of a semiconductor film prepared under the same conditions as in samples Nos. A-3, A-8 in Examples 1 and 2, a thin film transistor (hereinafter abbreviated as TFT) as shown in Fig. 3 was prepared. After deposition of a Si semiconductor polycrystalline layer 202 as shown in Fig. 2 with a film thickness of 0.5 µm on a glass (Coring #7059) base plate 201 under the above conditions, a TFT was prepared by use of the process for preparation of the upper gate coplanar TFT. First, according to the glow discharge method, a n+ layer (specific resistivity σ ≃ 1 Ω·cm) which is the ohmic contact layer 303 doped with P was deposited to a thickness of 100 nm (1000 Å), and then an active layer 302 was remained by photolithography, followed by etching of the channel portion 306 to form the above contact layer 303. Then, by use of the glow discharge method, NH₃ and SiH₄ were decomposed to deposit a Si-N-H film with a film thickness of 300 nm (3000 Å), dielectric constant of 6.7 and a dielectric strength 3 x 10⁶ V/cmV FB ≃ 0 V as the insulating layer 304 at a substrate temperature of 200 °C. Then, contact holes for source and drain are opened, Al was deposited to 500 nm (5000 Å) by vacuum vapor deposition as the upper electrode, and the source electrode 307, the gate electrode 309 and the drain electrode 308 were respectively formed by photolithography. (The gate width W and the gate length L were respectively 600 µm and 20 µm) (The respective TFT samples are referred to as Nos. 3A and 8A.) The characteristics when the drain electrode 308 was earthed and various + ○ voltages were applied on the source electrode 307 and the gate electrode 309 were measured. In the drain current I D - drain voltage V D characteristic, good saturation characteristics were obtained in both Nos. 3A and 8A to give a high current of 3 x 10⁻⁴ A at a gate voltage of 10 V and a drain voltage of 10 V. The TFT characteristics obtained from the results of measurement of the drain current I D at various gate voltage V D are shown in Table 3A. The TFT by use of the film as obtained above was found to have good characteristics. Some examples are shown below where heating or irradiation with electromagnetic wave such as light or microwave or with electron beam is utilized. First, method for preparing each sample are summarized below. A silicon thin film was formed on a substrate of a flat plate glass substrate (#7059, produced by Corning Co.) by means of the device shown in Fig. 1. By use of SiF₄ gas as the starting gas for formation of radicals containing silicon and halogen, this was permitted to flow into the reaction furnace maintained at 1100 °C to be decomposed, followed by release through the introducing pipe 102 into the acting chamber 108. At the same time, H₂ gas was permitted flow into the introducing pipe 103 and a microwave of 2.45GHz was introduced at a power of 0.5 W/cm² into said introducing pipe 3 to effect discharging to decompose H₂, followed by release into the acting chamber 108. The substrate temperature was maintained at 250 °C. Further, at the same time F₂ was permitted to flow through the introducing pipe 111, and microwave of 2.45 GHz was discharged at a power of 0.7 W/cm², followed by release into the acting chamber 113. By varying the flow rate ratios of F₂/Si₂F₆ as 5/100, 20/100, 30/100, 60/100, 80/100 (unit SCCM), and a pressure of 67 Pa (0.5 Torr) was maintained for 1 hour in each case to obtain the films having the characteristics as shown in Table 1B. Example 4 First, as shown in Example 2, under the same condition as in sample No. B-3, a polycrystalline film 202 100 nm((1000 Å) of film thickness) was formed on a glass substrate 201. A polycrystalline film with the great grain size and best orientation is prepared to be subjected to the following treatment. The substrate sample No. B-3 was delivered from the reaction chamber 402 to the annealing chamber 403 as shown in Fig. 4, and annealing was effected at a substrate temperature of 200 °C in H₂ of 27 Pa (0.2 Torr) by use of Ar ion laser, through the quarts window 404, at an output of 1 W at a scanning speed of 50 cm/sec with a beam diameter on the sample of 50 µm with a pitch of scanning of 35 µm. As the result, the crystal grain size was enlarged from 230 (2300 Å) on an average to 2 µm on an average. Also, according to X-ray diffraction measurement, the intensity of peak at the orientation face of (2,2,0) corresponding to the face direction (1,1,0) was increased to 5-fold or more. Further, the sample after completion of annealing was returned to the reaction chamber 402, and a polycrystalline film 503 was deposited to 400 nm (4000 Å) on a polycrystalline film 502 under the same condition at in the sample No. B-3 in the same Table 1B as described above. Thhis is shown in Fig. 5. In Fig. 5, 501 and 502 correspond to 201 and 202, respectively. As the result, a polycrystalline film 503 with an average grain size of 3 µm was obtained. The film surface was flat with unevenness difference of 10 nm (100 Å) or less, and the drift mobility was measured to be 330 cm²/v·s. Example 5 A polycrystalline film of 100 nm (1000 Å) was deposited under entirely the same conditions as in Example 4, i.e. the same condition as in sample No. 3 in Table 1B, and the sample was delivered into the annealing chamber 403, where ArF excimer laser with wavelength of 193 nm and pulse width of 30 nsec was irradiated through the quarts window 404 at 210 mJ/cm² and 100 pulses onto the sample maintained at 250 °C. As the result, the grain size of the polycrystalline film was grown to 1 µm or more on an average. Next, as the result of further deposition of a polycrystalline film of 400 nm (4000 Å) under the same conditions as in Example 4, a polycrystalline film with unevenness of the film surface of 8 nm (80 Å) or less, an average grain size of 1.5 µm or more and mobility of 180 cm²/v·s was obtained. Example 6 As shown in Fig. 6, on a part of the side wall of the reaction chamber in the experimental device shown in Fig. 1 is mounted a quarts window, a halogen lamp 604 is externally arranged and the device is converted so that the light is condensed linearly with a width of 1 mm or less in the direction perpendicular to the moving direction by the roller on the substrate. By means of the device shown in Fig. 1 which is converted as shown in Fig. 6, a polycrystalline film was deposited under the same conditions as in sample No. B-3 in Table 13. During this operation, while the halogen lamp 604 was irradiated simultaneously with deposition and the sample was moved reciprocally by a roller at 2 mm/sec the film was formed. The temperature of the sample surface on which the halogen lamp light was condensed during this operation was 600 °C. According to the above method, a polycrystalline film was deposited to thickness of 500 nm (5000 Å). As the result, a polycrystalline film with crystal grain sizes of 3 µm on an average were obtained, with the unevenness on the surface being 10 nm (100 Å) or less and mobility being 380 cm²/v·s. Example 7 In the device shown in Fig. 1, a tungsten wire heater was arranged perpendicularly to the moving direction of the sample by the roller at a distance of 3 mm from the substrate surface. The wire heater was heated to 850 °C, and a polycrystalline film of 500 nm (5000 Å) was deposited on the substrate under the same conditions as in sample No. B-3 in Table 1B, while the sample was moved by the roller at 1.5 mm/sec. As the result, the crystal grain size was 2 µm on an average, the surface unevenness 10 nm (100 Å) or less and mobility 290 cm²/v·s. Example 8 Under the entirely the same conditions as in sample No. B-3 in Table 1B, a polycrystalline Si of 500 nm (5000 Å) was formed on a glass substrate. After completion of deposition, the sample was transferred into an electron beam irradiation device shown in Fig. 7. The electrons coming out from the electron gun 701 are irradiated through the deflecting electrodes 703a, b and control electrodes 702a, 702b as accelerated converged beam of electrons on the sample 704. An electron beam narrowed to a beam current of 2 mA and a beam diameter of 100 µm at acceleration voltage of 7KV was irradiated onto the sample 700 maintained at a substrate temperature of 350°C, and scanned at a scanning speed of 400 mm/sec and a line delivery pitch of 50 µ in a reduced pressure of 10⁻⁵ Pa (10⁻⁷ Torr). As the result, a polycrystalline film with an average crystal grain size of 1 µm, surface unevenness of 20 nm (200 Å) or less and mobility of 160 cm²/v·s was obtained. Example 9 Under the entirely same conditions as in sample No. B-3 in Table 1, polycrystalline Si film of 500 nm (5000 Å) was formed on a glass substrate. The sample 802 was placed on the heater 801 fixed at the lower portion as shown in Fig. 8 in hydrogen gas of 13 Pa (0.1 Torr). While the heater 803 movable at the upper portion was moved at 1 mm/sec, heating was performed. During this operation, the heater fixed at the lower portion was maintained at 600 °C, the heater movable at the upper portion at 1100 °C. And the distance between the heater movable at the upper portion and the sample 802 surface was made 2 mm. As the result, a polycrystalline film with an average crystal grain size of 1 µm or more, surface unevenness of 15 nm (150 Å) or less and mobility of 180 cm²/v.s In the above Examples in which treatment to enlarge crystal grain size was carried out by heating or light irradiation, polycrystalline semiconductor Si film was grown on a glass substrate, but it is also possible to form an insulating film such as silicon nitride film, silicon oxide film by the glow discharge method, etc., and permit polycrystalline semiconductor Si film to grow on the insulating film. Also, when annealing is effected after film formation, it is also possible to perform laser annealing, electron beam annealing, etc., only on the semicnductor passage portion after formation of a device such as TFT. Of course, film forming conditions, various annealing methods, conditions, etc., are not limited to those as shown in the above examples. Example 10 By means of the device shown in Fig. 9 using a flat plate glass substrate (#7059 produced by Corning Co.) as the substrate, a polycrystalline silicon film was formed on said substrate. That is, a substrate (#7059) 903 was placed on a supporting stand 902, and the deposition chamber 901 was internally evacuated by means of an evacuation device to be reduced in pressure to about 10⁻⁴ Pa (10⁻⁶ Torr). H₂ gas was introduced from the bomb 906 for gas feeding at 50 sccm through the gas introducing pipe 925 into the activation chamber (B) 923. H₂ gas, etc., introduced into the activation chamber (B) was activated by the microwave plasma generating device 922 to be converted to active hydrogen, etc., and the active hydrogen, etc., were introduced through the introducing pipe 924 into the film forming chamber 901. On the other hand, SiF₄ gas was introduced at 20 sccm through the gas introducing pipe 512 into the activation chamber (A) 514 was activated by means of the microwave plasma generating device 513 and introduced through the introducing pipe 512 into the film forming chamber 501. Further, F₂ gas was introduced as the etching gas at 10 sccm through the gas introducing pipe 526 into the film forming chamber 501. While the pressure in the film forming chamber 501 was maintained at 3 Pa (0.02 Torr), the light from the 1KW Xe lamp was irradiated vertically onto the substrate 503 previously heated to 350°C by the heater 104 to deposit a polycrystalline silicon film by effecting mutual chemical reaction of the activated species, and at the same time form F* by activation of F₂ gas by the above mentioned photoirradiation, thereby effecting etching simultaneously with film formation of said polycrystalline silicon film by utilizing the difference in etching speed depending on the crystal faces, to form a polycrystalline silicon film with a strong orientation in a specific direction. At this time, the difference in etching speed depending on the crystal face was (1,0,0) > (1,1,1) > (1,1,0), whereby a polycrystalline silicon film having (1,1,0) face as the main crystal face was formed. That is, when the formed polycrystalline silicon film was evaluated by X-ray diffraction, the peak intensity at the crystal angle (2ϑ) of 47.3 degree reflecting the (1,1,0) face exhibited a value which was 7 to 10-fold of the peak intensity at the crystal angles (2ϑ) of 28.4 degree and 69.2 degree reflecting respectively the (1,1,1) face and (1,0,0) face. Further, the crystal grain size was observed to be 1.2 µm by a transmission type electron microscope. Also, when the above deposited film was analyzed by FT-IR, a weak peak was recognized in the vinicity of 2000 cm⁻¹, and hydrogen content was found to be 0.2 atomic%. Next, the polycrystalline film sample obtained was placed in a vapor deposition tank, and after formation of a comb-type Al gap electrode (length 250µm, width 5 mm) under an vacuum degree of 10⁻³ Pa (10⁻⁵ Torr), dark current was measured at an application voltage of 10 V to determine the dark electroconductivity σd for evaluation of the polycrystalline silicon. The film forming conditions as described above and the evaluation results of the polycrystalline silicon film are respectively shown in Table 1C and Table 2C. Example 11 Films were formed under the same conditions as in Example 10 except for varying the gas species and flow rates as shown in Table 3C. The evaluation results are shown in Table 4C. Example 12 Films were formed under the same conditions as in Example 10, except for introducing doping gases into the activation space (A) under the conditions shown in Table 5C. The evaluation results are shown in Table 6C. Example 13 Films were formed under the same conditions as in Example 10, except for introducing halogen containing gases into the film forming space under the conditions shown in Table 7C. The evaluation results are shown in Table 8C. Example 14 Films were formed under the same conditions as in Example 10 except for varying the discharging powers in the activation space (A) and the activation space (B) as shown in Table 9. The evaluation results are shown in Table 10C. Example 15 Films were formed under the same conditions as in Example 10 except for varying the substrate temperature as shown in Table 11C. The evaluation results are shown in Table 12C. Example 16 Films were formed under the same conditions as in Example 10 except for varying the inner pressure as shown in Table 13C. The evaluation results are shown in Table 14C. Example 17 Films were formed under the same conditions as in Example 10, except for varying the output of light source as shown in Table 15C. The evaluation results are shown in Table 16C. Example 18 Fig. 10 is a schematic partial perspective view showing the structure of a thin film transistor (hereinafter abbreviated as TFT) of which semiconductor part is constituted of a polycrystalline silicon formed according to the method for forming deposited film of the present invention. The polycrystalline silicon TFT 1000 shown in Fig. 10 is constituted to have a structure which is formed by laminating successively a gate electrode 1001, an electrically insulating layer 1004 so as to cover over said gate electrode 1001 on a substrate 1006 comprising glass, ceramic, etc., and a semiconductor layer 1005 comprising a polycrystalline silicon, and on the surface 1008 of the semiconductor layer 1005 are provided a first n⁺ layer 1007-1 and a second n⁺ layer 1007-2 in a juxtaposed relationship apart from each other, and further a source electrode 1002 is provided on the first n⁺ layer 1007-1 and a drain electrode 1003 on the second n⁺ layer 1007-2, respectively. The first n⁺ layer 1007-1 and the second n⁺ layer 1007-2 provided in contact on the surface (clean surface) 1008 on the semiconductor layer 1005 are formed after formation of the semiconductor layer 1005 without exposing said layer surface 1008 to the atmosphere or oxygen. In this Example, the distance L between the source electrode 1002 and the drain electrode 1003 is 50 µm and the length Z of the source electrode 1002 and the drain electrode 1003 is 10 mm. The semiconductor layer 1005 in this example was formed under the same condition as sample No. C-1 (which corresponds to C-9-1), C-2-2 (which corresponds to C-9-2). The characteristics when various + ○ voltages were applied on the source electrode and the gate electrode with the drain electrode being earthed were measured. In the drain current I D -drain voltage V D characteristics, good saturation characteristics were obtained in both Nos. C-9-1, C-9-2, and high current of 5 x 10⁻⁴ A was obtained at a gate voltage 10 V and a drain voltage 10 V. The TFT characteristics obtained from the results of measurement of drain current I D at various gate voltage V G are shown in Table 17C. The TFT by use of the polycrystalline silicon film obtained as described above was found to exhibit good characteristics. Example 19 First, as shown in Fig. 11, a polycrystalline film 12 was deposited to 100 nm (1000 Å) on the glass substrate 1101 according to the process as described above under the conditions in Table 1C. Next, as shown in Fig. 12, Xe lamp was replaced with Ar ion laser, at a substrate temperature of 200 °C by use of Ar ion laser in H₂ of 67 Pa (0.2 Torr), through the quartz window 1201, annealing was effected at an output of 1 W with a beam diameter of 50 µm at a scanning speed of 50 cm/sec and a pitch of scanning of 35 µm. As the result, the crystal grain size was enlarged from 210 nm (2100 Å) on an average to 2 µm on an average. Also, according to X-ray diffraction measurement, the intensity peak on the orientation face of (220) was found to be increased to 5-fold or more. Further, after completion of annealing, Ar ion laser was returned to Xe lamp, and a polycrystalline film was deposited to 400 nm (4000 Å) under the same conditions in Table 1C. The same state as this state of the sample is shown in Fig. 4. As the result, a polycrystalline film with grain sizes of 3 um or more on an average was obtained. The film surface was flat with a different in unevenness of 10 nm (100 Å) or less, and the drift mobility was measured to be 330 cm²/v.s. Example 20 According to the same conditions as in Example 19, a polycrystalline film 502 of 100 nm (1000 Å) was deposited, and with removal of Xe lamp, ArF excimer laser with a wavelength of 193 nm and a pulse width of 30 nsec was irradiated on a sample maintained at 250 °C at 210 mJ/cm² and 100 pulses. As the result, the grain size of the polycrystalline film was grown to 1 um or more on an average. Next, as the result of deposition of a polycrystalline film under the same conditions as in Example 19 to 400 nm (4000 Å), a polycrystalline film with unevenness of the film surface of 8 nm (80 Å) or less, an average grain size of 1.5 µm or more and a mobility of 180 cm²/v·s was obtained. Example 21 In the device in Fig. 9, Xe lamp 1301 and halogen lamp 1302 were mounted at the same time, and the halogen lamp light was condensed linearly with a width of 1 mm or less in the direction perpendicular to the moving direction by the roller on the substrate. This is shown in Fig. 13. By means of the device shown in Fig. 5, a polycrystalline film was deposited under the same conditions as in Table 1C. During this operation, the halogen lamp 1302 was irradiated simultaneously with deposition and the sample was moved by a roller at 2 mm/sec. The temperature of the sample surface on which the halogen lamp light was condensed during this operation was 600 °C. According to the above method, the sample was moved reciprocally by the roller to deposit a polycrystalline film of 500 nm (5000 Å). As the result, a polycrystalline film with crystal grain sizes of 3 µm on an average were obtained, with the unevenness on the surface being 10 nm (100 Å) or less and mobility being 380 cm²/v·s. Example 22 In the device shown in Fig. 9, a tungsten wire heater was arranged perpendicularly to the moving direction of the sample by the roller at a distance of 3 mm from the substrate surface. The wire heater was heated to 850 °C, and a polycrystalline film of 500 nm (5000 Å) was deposited under the same conditions as in Table 1C in Example 19, while the sample was moved by the roller at 1.5 mm/sec. As the result, the crystal grain size was 2 µm on an average, the surface unevenness 10 nm (100 Å) or less, and mobility 290 cm²/v.s. Example 23 Under the same conditions as in Table 1C in a polycrystalline Si of 500 nm (5000 Å) was formed on a glass substrate. After completion of deposition, the sample was transferred into an electron beam irradiation device shown in Fig. 7. The electrons coming out from the electron gun 701 were irradiated through the deflecting electrodes 703a, b and control electrodes 702a, b and 704a, b as accelerated converged beam of electrons on the sample. An electron beam narrowed to a beam current of 2 mA and a beam diameter of 100 µm at acceleration voltage of 7 KV was irradiated onto the sample maintained at a substrate temperature of 350 °C, and scanned at a scanning speed of 400 mm/sec and a line delivery pitch of 50 µm in a reduced pressure of 10⁻⁵ Pa (10⁻⁷) Torr). As the result, a polycrystalline film with an average crystal grain size of 1 µm, surface unevenness of 20 nm (200 Å) or less and mobility of 160 cm²/v·s was obtained. Example 24 Under the entirely same conditions as in Table 1C, a polycrystalline Si film of 500 nm (5000 Å) was formed on a glass) substrate, and then with the sampel 802 being placed on the heater 801 fixed at the lower portion as shown in Fig. 8 in hydrogen gas of 13 Pa (0.1 Torr), the heater 803 movable at the upper portion was moved at 1 mm/sec. During this operation, the heater fixed at the lower portion was maintained at 600 °C, the heater movable at the upper portion at 1100 °C. And the distance between the heater movable at the upper portion and the sample surface was made 2 mm. As the result, a polycrystalline film with an average crystal grain size of 1 µm or more, surface unevenness of 15 nm (150 Å) or less and mobility of 180 cm²/v·s was obtained.

Claims: A process for forming a silicon containing crystalline deposited film which process comprises the steps of: providing in a deposition chamber a substrate, a major surface of which is exposed; introducing separately into said deposition chamber previously activated chemically mutually reactive first and second species and causing these to react and deposit a silicon containing crystalline film upon said major surface of the substrate, said activated first species being formed by the decomposition of a compound containing both silicon and a halogen; during the deposition of said film heating said deposited film by heating means; and exposing the deposited film growth surface to a gaseous etchant to effect crystal growth in a preferential face direction, whilst increasing etchant activity by irradiating this gaseous etchant with photo-energy. A process as claimed in claim 1 wherein said activated first species is formed by the decomposition of a chain halogenated silane represented by Si u Y 2u+2 , wherein u is an integer of 1 or more and Y is at least one element selected from F, Cl, Br or I. A process as claimed in claim 1 wherein said activated first species is formed by the decomposition of a chain or cyclic halogenated silane represented by the formula Si u H x Y y , wherein u , x and y are integers of 1 or more, x + y = 2u or x + y = 2u +2, and Y is at least one element selected from F, Cl, Br or I. A process as claimed in claim 1 wherein either hydrogen or a halogen is used in addition to said compound during the decomposition thereof. A process as claimed in claim 1 wherein said activated second species is formed from either hydrogen gas or a halogen gas. A process as claimed in claim 1 wherein said activated first and second species are introduced into the film forming space at flow rates in a ratio of between 10:1 and 1:10. A process according to claim 1 wherein said activated first species is formed by the decomposition of said compound containing silicon and a halogen in the presence of a compound containing an element for doping the film. A process as claimed in claim 1 wherein a compound containing an element for doping the film is present with another chemical substance during formation of said activated second species. A process as claimed in claim 1 wherein an activated species that is formed from a compound containing an element for doping the film is also introduced into said film forming space during film deposition. A process as claimed in any one of the preceding claims wherein said substrate is of flat plate glass. A process as claimed in any one of the preceding claims 1 to 9 wherein the exposed surface of said substrate is comprised of insulating film material. A process as claimed in claim 11 wherein the insulating film is of either silicon nitride or silicon oxide.

Inventors: HIRAI, YUTAKA, MATSUYAMA, JINSHO, SHIRAI, SHIGERU
Applicants: CANON KABUSHIKI KAISHA
Application year: 1987
Main classification: H01L21
IPC codes: C23C16, H01L21