CN103572262A - Light CVD film manufacturing method and light CVD film manufacturing apparatus - Google Patents
Light CVD film manufacturing method and light CVD film manufacturing apparatus Download PDFInfo
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 80
- 239000007789 gas Substances 0.000 claims abstract description 127
- 238000006243 chemical reaction Methods 0.000 claims abstract description 115
- 230000003287 optical effect Effects 0.000 claims description 92
- 238000009434 installation Methods 0.000 claims description 55
- 230000005540 biological transmission Effects 0.000 claims description 39
- 230000008676 import Effects 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 37
- 239000000758 substrate Substances 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 230000001678 irradiating effect Effects 0.000 claims description 4
- 238000009826 distribution Methods 0.000 description 14
- NJPPVKZQTLUDBO-UHFFFAOYSA-N novaluron Chemical compound C1=C(Cl)C(OC(F)(F)C(OC(F)(F)F)F)=CC=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F NJPPVKZQTLUDBO-UHFFFAOYSA-N 0.000 description 10
- 239000011521 glass Substances 0.000 description 8
- 230000004888 barrier function Effects 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 238000005755 formation reaction Methods 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
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- 230000008901 benefit Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 3
- 239000005001 laminate film Substances 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
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- 239000000203 mixture Substances 0.000 description 2
- WSPOQKCOERDWJQ-UHFFFAOYSA-N 2-methyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound C[SiH]1O[SiH2]O[SiH2]O[SiH2]O1 WSPOQKCOERDWJQ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000010748 Photoabsorption Effects 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
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- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/48—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating by irradiation, e.g. photolysis, radiolysis, particle radiation
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/52—Controlling or regulating the coating process
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
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- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/02—Details
- H05B33/04—Sealing arrangements, e.g. against humidity
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- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
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Abstract
The invention provides a manufacturing method and a manufacturing apparatus of a light CVD film, which can easily improve the uniformity of the film thickness. The manufacturing method of the light CVD film includes a step (a) for guiding raw gases of the light CVD film to a reaction chamber of the light CVD film to make the reaction chamber achieve set pressure; a step (b) for stopping the guiding of the raw gases into the reaction chamber and the exhausting of the raw gases out of the reaction chamber to irradiate light to the reaction chamber after step (a), and a step (c) for stopping the irradiation after the step (b) and then exhausting the reaction chamber, and the steps (a)-(c) can be repeated for many times.
Description
Technical field
The present invention relates to the manufacture method of optical cvd film and the manufacturing installation of optical cvd film.
Background technology
Organic electroluminescent (being designated as below organic EL) element has the lot of advantages such as reduce power consumption, luminous, high-speed response, is developing towards the application of flat-panel monitor (FPD), set lights.In addition, by using the flexible base, boards such as resin substrate (comprising resin film), produced crooked, gently, the new value added such as easy fracture not, also studying organic EL to the application of flexible apparatus.
While contacting with moisture, oxygen due to organic EL, cause that luminous efficiency reduces, the life-span is deteriorated, so need to just get rid of moisture, oxygen from manufacturing processed.On the other hand, in the flexible base, boards such as resin substrate, need to suppress to follow the caused dimensional variations of moisture absorption.According to above reason, organic EL is formed with barrier film at the surperficial back side of its resin substrate.At this, barrier film refers to and prevents that moisture, oxygen from entering the film of organic EL, resin substrate from outside, in order to suppress the diffusion of moisture, oxygen, uses the large film of film density.As the concrete material of barrier film, use silicon nitride film (being denoted as below Si nitrided film) or pellumina etc.
For the sealing membrane of organic EL, prevent that the diffusion of moisture, oxygen from, from needless to say, also requiring: (1) film formation at low temp (preventing that organic EL is deteriorated); (2) low damage (preventing that organic EL is deteriorated); (3) low-stress, low Young's modulus (preventing from peeling off); (4) high-transmission rate (preventing deterioration in brightness) etc.Corresponding to this, there are the following problems for each material of above-mentioned barrier film: because film hard (Young's modulus is large), membrane stress are also large, so can occur while using thick film that film peels off or crackle.
So, as the structure of the sealing membrane of organic EL, cause that the most what gaze at is laminate film structure.This laminate film structure is the structure that has formed a plurality of films that multilayer object is different, known by barrier film with relax the stacked a plurality of structure of film (buffer film) of barrier film stress.The desired project of buffer film is: the planarization of substrate, for the impact that suppresses to be attached to surperficial foreign matter good and film is soft (Young's modulus is little) and membrane stress is little in landfill performance.As the concrete material of buffer film, there is silicon oxide film that contains carbon etc.
In patent documentation 1, the sealing membrane of such laminate film structure is disclosed.As the manufacture method of sealing membrane, the various films such as plasma CVD method, optical cvd method, sputtering method, vapour deposition method have been proposed, as its typical example, form for example continuously barrier film and buffer film use vacuum ultraviolet optical cvd method.
As the manufacturing installation of optical cvd film, the manufacturing installation that has patent documentation 2 and 3 to record.In the manufacturing installation of patent documentation 2, from the horizontal importing unstripped gas of sample (object being treated).In addition, in the manufacturing installation of patent documentation 3, a plurality of by the transmission window on sample top is divided into, and a plurality of gas introduction ports are set between each transmission window, thus from the top of sample, import unstripped gas.
Patent documentation 1: TOHKEMY 2005-63850 communique
Patent documentation 2: TOHKEMY 2005-340702 communique
Patent documentation 3: TOHKEMY 2012-12628 communique
Summary of the invention
General CVD device possesses introducing mechanism, gas exhaust mechanism, the automatic pressure of unstripped gas and controls (APC) mechanism, by following operation, forms optical cvd film.(1) via gas, import valve and import a certain amount of unstripped gas to the reaction chamber after vacuum exhaust.(2) adjust APC valve, pressure transmitter is set to the pressure of regulation.(3) light vacuum ultraviolet ray lamp, carry out rayed and start film forming.(4) after having reached specific time, extinguish vacuum ultraviolet ray lamp, reaction chamber is carried out to vacuum exhaust.At this, in operation (3), while import, unstripped gas is controlled free air delivery so that the air pressure of reaction chamber reaches constant.Therefore, in reaction chamber, having the mobile of gas is the concentration distribution of unstripped gas.Because the film forming speed of CVD method also depends on gas concentration, therefore, for film uniformity is improved, need to make gas concentration be evenly distributed.Particularly, in optical cvd method, because the direct absorb light of unstripped gas is decomposed, reacted, so film forming speed presents the tendency of the mobile and gas concentration that greatly depends on gas.
So dependent concrete example is illustrated in Fig. 7.Fig. 7 shows in the manufacturing installation of optical cvd film that has in the horizontal gas introduction port as shown in patent documentation 2, film uniformity while forming optical cvd film on the sample of diameter 300mm, shows especially and makes the constant and film uniformity while only changing the air pressure of reaction chamber of the feed rate of unstripped gas.As can be seen from Figure 7, along with air pressure changes, there is very large change in film uniformity.Shown in Fig. 8 when air pressure is 60Pa the film thickness distribution (%) during film forming.The distribution with respect to average film thickness in numeric representation sample, each isocontour interval is corresponding with 2% thickness deviation.Arrow in figure represents the flow direction of the unstripped gas on sample.Show thickness and import side (the lower-left side of Fig. 8) to the tendency of exhaust side (upper right side of Fig. 8) thickening from gas.So, the thickness that shows optical cvd film depends on the feature of flowing of unstripped gas and gas concentration greatly.
Even in such film, if the such undersized sample of 10mm * 10mm level for example, the optimizing by air pressure or sample is rotated, also has the leeway of guaranteeing to a certain extent film uniformity.But, when the size of sample as the flat glass substrate in the 8th generation (2200mm * 2500mm) becomes large, be difficult to only by the optimizing of pressure, guarantee film uniformity.In addition, make large-size glass substrate rotate film forming also unrealistic.
On the other hand, the manufacturing installation of the optical cvd film of patent documentation 3 becomes the structure that more large-scale glass substrate is also easily tackled.The result that the Place Attachment of the thickness of the manufacturing installation that present inventor shown in Fig. 9 records patent documentation 3 is studied.Fig. 9 means that thickness is with respect to the figure of the distribution of the flow direction of unstripped gas.Be made as from the top base feed gas of the G1～G5 with constant interval configuration.Be supplied to the unstripped gas for the treatment of chamber, film forming speed increases along with the flow direction of the gas towards utilizing light to decompose/react, and when gas is consumed, film forming speed reduces.That is to say, the thickness of institute's film forming presents sinusoidal wave distribution for take the flow direction of gas introduction part as basic point to gas.In Fig. 9, the film thickness distribution that the gas introduction port by odd indexed (G1, G3, G5) is caused represents with fine line, and the film thickness distribution that the gas introduction port by even number sequence number (G2, G4) is caused represents with dotted line.By heavy line, represented fine rule and dotted line to be added the thickness obtaining, this thickness becomes the thickness on actual sample.; if be made as film thickness distribution, with respect to the flow direction of gas, present the distribution of sine wave shape, in the position of this sinusoidal wave semi-period, gas introduction port is set, if so; even if, in large-size glass substrate, also can guarantee film uniformity to a certain degree.The gas that Fig. 9 only shows the flow direction (directions X) of gas imports position (1 dimension represents), but because in fact also need the importing position of gas in the vertical direction of the flow direction with gas (Y direction), so importing position, gas becomes the 2 dimension configurations that are provided with certain intervals.
As the explanation of carrying out above, according to import the manufacturing installation of the optical cvd film of unstripped gas shown in patent documentation 3 from the top of sample, compare with the manufacturing installation from the optical cvd film of horizontal importing unstripped gas shown in patent documentation 2, can improve the homogeneity of thickness.Yet in the method shown in patent documentation 3, the configuration of gas introduction port has affected film uniformity greatly.
That is, because needs import gas between transmission window and transmission window, so restricted in the shape of transmission window, size, configuration.In other words, there are the following problems for the film deposition system of the optical cvd film of patent documentation 3: only can import the corresponding scope research in position filming condition with gas.
Thus, even if even if need as shown in patent documentation 2 the homogeneity top from sample as shown in patent documentation 3 that also can improve thickness from horizontal importing unstripped gas to import the technology that unstripped gas also can reduce the restriction of configuration gas introduction port.Based on the above, the object of the present application is, a kind of manufacture method and manufacturing installation that easily further improves the inhomogeneity optical cvd film of thickness is provided.
Representational means in the means of dealing with problems of illustration the present application, be a kind of manufacture method of optical cvd film, it is characterized in that, comprising: operation (a), unstripped gas to forming the reaction chamber lead-in light cvd film of optical cvd film, makes reaction chamber reach specified pressure; Operation (b), in operation (a) afterwards, stops unstripped gas, to the importing of reaction chamber and unstripped gas from the exhaust of described reaction chamber, to reaction chamber, irradiating light; And operation (c), in operation (b) afterwards, stop described irradiation, then reaction chamber is carried out to exhaust, by operation (a)～operation, (c) is repeated multiple times.
In addition, a kind of manufacturing installation of optical cvd film, is characterized in that, has: the reaction chamber that substrate is set; Light source portion from the external irradiation light of reaction chamber; Make light to the transmission window of reaction chamber transmission; The 1st gas imports valve, and it is to the unstripped gas of reaction chamber lead-in light cvd film; The 1st vent valve, it is connected with reaction chamber, and reaction chamber is carried out to exhaust; With the 2nd vent valve, it is connected with reaction chamber via the 1st vent valve, and reaction chamber is carried out to exhaust.
In addition, a kind of manufacturing installation of optical cvd film, is characterized in that, has: the reaction chamber that substrate is set; Light source portion from the external irradiation light of reaction chamber; Make light to the transmission window of reaction chamber transmission; The 1st gas imports valve, and it is to the unstripped gas of reaction chamber lead-in light cvd film; A plurality of the 1st vent valves, it is connected with reaction chamber, and reaction chamber is carried out to exhaust; With the 2nd vent valve, it is connected with reaction chamber via a plurality of the 1st vent valves, and diameter is larger than the diameter of a plurality of the 1st vent valves.
According to the present application, can provide a kind of manufacture method and manufacturing installation that easily further improves the inhomogeneity optical cvd film of thickness.
Accompanying drawing explanation
Fig. 1 means the figure of manufacturing installation of the optical cvd film of embodiment 1.
Fig. 2 means the figure of manufacture method of the optical cvd film of embodiment 1.
Fig. 3 means the dependent figure of the film forming speed of optical cvd film to the pressure of reaction chamber.
Fig. 4 means the figure of manufacturing installation of the optical cvd film of embodiment 2.
Fig. 5 means the figure of manufacturing installation of the optical cvd film of embodiment 3.
Fig. 6 means the figure of manufacture method of the optical cvd film of embodiment 3.
Fig. 7 is the figure of the problem that explanation is relevant to the film uniformity of optical cvd film.
Fig. 8 is the figure of the problem that explanation is relevant to the film thickness distribution of optical cvd film.
Fig. 9 is the figure of the problem that explanation is relevant to the film thickness distribution of optical cvd film.
Figure 10 means the figure of the film thickness distribution of the optical cvd film that the manufacture method by embodiment 1 produces.
The explanation of Reference numeral
101,201,501: reaction chamber,
102,202,502: sample pedestal,
103,203,503: sample (glass substrate),
104,204,504: transmission window (synthetic quartz),
105,205,505:VUV lamp,
106,206,506: unstripped gas imports valve,
107,207,507: reaction chamber baroceptor,
108,208,508: exhaust pipe arrangement,
109,209,509: vent valve,
110,111,210,510:APC valve,
113, nitrogen imports valve,
114,214,514: vacuum pump,
115,251: hog frame
Embodiment
[embodiment 1]
Fig. 1 is the summary of manufacturing installation of the optical cvd film of embodiment 1.Device is by the reaction chamber 501 that forms optical cvd film, sample pedestal 502, sample 503, transmission window 504, vacuum ultraviolet ray (VUV:Vacuum Ultraviolet) lamp 505, the unstripped gas of the unstripped gas of lead-in light cvd film imports valve 506, chamber pressure sensor 507, for the exhaust pipe arrangement 508 that unstripped gas is discharged from reaction chamber, vent valve 509, automatic pressure is controlled (APC) valve (APC=Auto Pressure Control) 510, and vacuum pump 514 forms, the manufacturing installation of the optical cvd film of recording with patent documentation 2 is same, unstripped gas imports valve 506 and is positioned at transversely with respect to sample 503.But, the invention of the present embodiment feature that possesses skills in the manufacture method of optical cvd film, the structure of the manufacturing installation of optical cvd film is not limited thereto.Same with the content that patent documentation 3 is recorded, by unstripped gas imports the manufacturing installation of optical cvd film of valve and the film of the optical cvd film of the present embodiment combines by being provided with up with respect to sample 503, can further improve the homogeneity of thickness.In the present embodiment, as VUV lamp 505, use Xe
2excimer lamp (wavelength=172nm), as unstripped gas, use organosilicon source OMCTS (Octo methyl cyclotetrasiloxane, octamethylcyclotetrasiloxane) to carry out film forming.But, although OMCTS is lifted, be an example, this is one of preference, unstripped gas is not limited to this unstripped gas.Gas as obtaining with OMCTS effect same, has TEOS (Tetra ethoxy silane, tetraethoxy) and oxygen, HMDSO (Hexa methyl disiloxane, hexamethyldisiloxane) etc.In addition, the wall of reaction chamber 501 and transmission window 504 are heated to 120 ℃ for adhering to of inhibited reaction thing.On the other hand, the temperature of sample pedestal 502 controls to 30 ℃ by water cooler.
As mentioned above, in optical cvd method, film forming speed depends on flowing and gas concentration of unstripped gas greatly.In other words, if flowing of not caused by the importing of the unstripped gas in reaction chamber or exhaust, gas concentration is evenly distributed, and film forming speed becomes even.Even in order to realize film forming speed, gas is being closed under the state at reaction chamber and irradiating light.For this reason, following method is effective: by repeatedly make pressure in reaction chamber reach the operation of desirable pressure, making to carry out light-struck operation of desirable time, the operation of carrying out vacuum exhaust under the mobile state stopping of unstripped gas, form thus optical cvd film.
Based on the above, the manufacture method of the optical cvd film of embodiment 1 is illustrated in Fig. 2.The manufacture method of the optical cvd film of Fig. 2 is characterised in that, comprising: operation (a), and the unstripped gas to forming the reaction chamber lead-in light cvd film of optical cvd film, makes reaction chamber reach specified pressure; Operation (b), in operation (a) afterwards, stops unstripped gas to the importing of reaction chamber and unstripped gas from the exhaust of reaction chamber, to reaction chamber, irradiates light; And operation (c), in operation (b) afterwards, stop irradiating, then reaction chamber is carried out to exhaust, by operation (a)～operation, (c) is repeated multiple times.
Shown in Figure 10 by the film thickness distribution of the optical cvd film of the manufacture method film forming of the present embodiment.Air pressure during rayed and Fig. 8 are made as 60Pa equally.The homogeneity of the thickness of the illustrated optical cvd film of Figure 10, compares tremendously and improves with Fig. 8.So, by carrying out the manufacture method of the optical cvd film of the present embodiment, can make the film uniformity of optical cvd film improve tremendously.
And then, while carrying out the film forming of optical cvd film by the manufacture method of the present embodiment, not only there is the large advantage that film uniformity improves, also there is the restriction of the importing position that can relax unstripped gas, relax the restriction that arranges of transmission window.
And then, more preferably, being further characterized in that, the specified pressure in operation (a) is less than the pressure of the film forming speed maximum that makes optical cvd film.In optical cvd method, every kind of gas all be there is to the pressure of the reaction chamber that makes film forming speed maximum.Fig. 3 illustrates this situation, and transverse axis is the pressure of reaction chamber, and the longitudinal axis is the film forming speed of optical cvd film.For gaseous species A, for about 70Pa, for gaseous species B, be for example about 100Pa, although the concrete pressure of reaction chamber is different, every kind of gas all existed to the pressure that makes the film forming speed of optical cvd film reach maximum reaction chamber, this point is common.This be because: in the film formation reaction of optical cvd film, due to the increase of raw gas concentration, decompose, speed of response is accelerated, film forming speed becomes large composition and the photoabsorption in unstripped gas becomes the light that ambassador must arrive sample substrate and reduces so that the composition that speed of response reduces coexists.Therefore,, when film forming speed presents peaked pressure and carries out film forming above in the situation that, the service efficiency of unstripped gas reduces.Its result, residual not for the unstripped gas of film formation reaction in reaction chamber, it makes transmission window fuzzy, becomes the reason that causes reaction efficiency to reduce.Thus, the pressure of the reaction chamber in operation (a), preferably " makes the pressure of the film forming speed maximum of optical cvd film " lower than this.
[embodiment 2]
In the above embodiments 1, the structure of manufacturing installation is not particularly limited.Yet, in the manufacture method of the optical cvd film of embodiment 1, owing to following operation that the valve of exhaust side is is repeatedly opened and closed at high speed (operation (a) and (c)), therefore think and when opening and closing, produce foreign matter.So, if having, manufacturing installation suppresses the inhibition unit that foreign matter produces, can further improve the homogenizing of thickness.Based on the above, in embodiment 2, explanation can further improve the manufacturing installation of the inhomogeneity optical cvd film of thickness.
The summary of the manufacturing installation of the optical cvd film of embodiment shown in Fig. 42.Fig. 4 is the manufacturing installation with the optical cvd film of large exhaust pipe arrangement 108 and 2 APC (APC:Auto Pressure Control) valve 110,111.Apparatus structure imports valve 106, chamber pressure sensor 107, exhaust pipe arrangement 108, vent valve 109, an APC valve 110, the 2nd APC valve 111, the 2nd pressure transmitter 112 for APC valve, nitrogen importing valve 113, vacuum pump 114 formations by reaction chamber 101, sample pedestal 102, sample 103, transmissive glass 104, vacuum ultraviolet ray (VUV:Vacuum Ultra violet) lamp 105, unstripped gas.The material of transmission window 104 is synthetic quartz and is divided into the size that can maintain physical strength.In the present embodiment, be made as the rectangular transmission window 104 of minor face=200mm and long limit=1500mm.Although enumerated the example of the structure (short side direction) of arranging 3 transmission window 104 in Fig. 4, as long as transmission window 104 and the size of the sample using are correspondingly increased.For example, if arrange the transmission window of 10 these sizes, glass substrate that just can corresponding the 6th generation size (1500mm * 1850mm).Between transmission window 104 and transmission window 104, the hog frame 115 that keeps transmission window 104 is set.The width of hog frame 115, fully maintaining physical strength and making on the uniform basis of light intensity distributions, preferably narrow as far as possible.In the present embodiment, in order to eliminate the impact of the shading light part of hog frame 115, be made as the structure that can make sample pedestal 102 work in 2 dimension directions.More than this working width is preferably the width of hog frame 115.In the present embodiment, on the short side direction of transmission window 104, be made as sample pedestal 102 is moved about at the interval of 50mm respectively with left and right.Direction and the width that moves about that sample pedestal 102 is moved about determine optimum value on the basis of having considered the shape of transmission window 104 and the width of hog frame 115.
At this, the film of the optical cvd film that the manufacturing installation by Fig. 4 carries out is described.This structure is characterised in that, APC valve forms by 2 grades that connect, and an APC valve 110 of prime links with pressure transmitter 112 with the 2nd APC valve with chamber pressure sensor 107 interlocks, the 2nd APC valve 111 of rear class.Formation imports the structure of having controlled the nitrogen of flow via gas trap 113 to the pipe arrangement between an APC valve 110 and the 2nd APC valve 111.
First, when opening gas and importing valve 106 and import unstripped gas to reaction chamber, output signal, so that chamber pressure sensor 107 and the 2nd APC valve reach uniform pressure with pressure transmitter 112, now, is opened nitrogen and with valve 113, is imported the nitrogen of regulation flow.Then, the pressure that has reached regulation in reaction chamber 101 is closed gas importing valve 106 afterwards, starts rayed.Now, because the front and back of an APC valve 110 are controlled as uniform pressure, so the mobile of the gas in reaction chamber stops.After having carried out the film forming of specified time, close valve 113 for nitrogen, make an APC valve 110 and the 2nd APC valve 111 open, carry out vacuumizing of reaction chamber 101 completely.By this operation repeatedly, carry out the film forming of optical cvd film.Although APC valve is depicted as to 2 grades being connected in series in Fig. 4, increases progression according to object and be certainly also fine.
So, the manufacturing installation of the optical cvd film of the present embodiment is characterised in that to have: the reaction chamber (101) that substrate is set; Light source portion (vacuum ultraviolet ray lamp 105) from the external irradiation light of reaction chamber; Make described light to the transmission window (104) of reaction chamber transmission; The 1st gas to the unstripped gas of reaction chamber lead-in light cvd film imports valve (106); Be connected the 1st vent valve (110) that reaction chamber is carried out to exhaust with reaction chamber; With via the 1st vent valve, be connected the 2nd vent valve (111) that reaction chamber is carried out to exhaust with reaction chamber.
The effect of this manufacturing installation is described below.As mentioned above, if vent valve is opened and closed, when opening and closing, produce foreign matter.Particularly, substrate size be the 8th generation grade large-scale manufacturing installation in, need larger exhaust capacity, need to reduce the conductivity of exhaust system.The conductive method that reduces exhaust system has multiple, but usual method is the method that increases the main valve of exhaust pipe arrangement, exhaust system.But if repeatedly open and close sharp so large vent valve, the amount that foreign matter produces is also just more.
Thus, wish to adopt the valve that can further suppress foreign matter generation.The example of enumerating as such valve is the APC valve illustrating in the present embodiment.APC valve due to can not be as diaphragm type valve with switching rapidly, so also can produce hardly foreign matter even if increase valve.But APC valve will stop exhaust completely and be difficult to textural, is difficult to make exhaust gas to stop completely in common structure.
On the other hand, according to the manufacturing installation of the present embodiment, by the combination of the 1st vent valve and the 2nd vent valve, the indoor gas of stopped reaction flows in fact.Therefore, for the 1st and the 2nd vent valve, can adopt the valve (for example APC valve) of more difficult generation foreign matter, compare with the manufacturing installation of explanation in embodiment 1, can further suppress the generation of foreign matter.The important part of the manufacturing installation of the present embodiment is: because the film uniformity of optical cvd film does not depend on the importing position of unstripped gas completely, so the degree of freedom of the setting position of gas trap is large, and film uniformity improves tremendously.In addition, by stoping the APC valve of gas to be arranged to connect more than 2 grades completely by being difficult to, the gas flow of essence that can stopped reaction chamber.Therefore, only by the action of APC valve, just can realize the high speed on-off action of exhaust side, so suppress turnout (throughput) reduction and suppress foreign matter to produce even if use large-scale plant also can realize.
And the manufacturing installation of the optical cvd film of the present embodiment is further characterized in that, the region between the 1st vent valve and the 2nd vent valve has the 2nd gas that imports nitrogen and imports valve (113).According to this structure, by making this region and reaction chamber isobaric, can make the flowing of gas in reaction chamber stop in fact.
As for monitoring the structure of the pressure of this region and reaction chamber, also have the 1st pressure transmitter (107) of pressure of assaying reaction chamber and the 2nd pressure transmitter (112) of the pressure in this region of mensuration, the 2nd gas imports valve and imports nitrogen so that the measured value of the 2nd pressure transmitter equates with the measured value of the 1st pressure transmitter.
In addition, by the 2nd vent valve is configured to by controlling from the signal of the 1st pressure transmitter, can make the pressure in reaction chamber more easily remain the pressure that is suitable for film forming.
As mentioned above, in the manufacturing installation of the optical cvd film of the present embodiment, the film uniformity of optical cvd film does not depend on the importing position of unstripped gas, therefore the 1st gas can be imported to valve and be arranged on substrate transversely.By this configuration, compare with the manufacturing installation of the optical cvd film of patent documentation 3, can further reduce the restriction condition of transmission window, gas introduction port, can improve the degree of freedom of device design.
In addition, in the structure shown in Fig. 4, show and only at 2 positions, exist unstripped gas to import valve 106, but gas imports valve 106, also can exist a plurality of.Equally, gas exhaust valve 109, APC valve 110,111 and pump also can exist a plurality of.In addition, in the present embodiment, as the example that more can suppress the valve that foreign matter produces than the valve of diaphragm type, enumerate APC valve, but so long as can play the valve of this effect, also can adopt other valve.
[embodiment 3]
In embodiment 3, use Fig. 5 and 6 pairs can further improve describing with embodiment 2 distinct portions in the manufacturing installation of inhomogeneity optical cvd film of thickness.
The manufacturing installation of the optical cvd film of the present embodiment shown in Fig. 5.The manufacturing installation of the optical cvd film of Fig. 5 consists of reaction chamber 201, sample pedestal 202, sample 203, transmissive glass 204, VUV lamp 205, unstripped gas importing valve 206, chamber pressure sensor 207, a plurality of exhaust pipe arrangement 208, a plurality of vent valve 209, APC valve 210, vacuum pump 214.At this, the manufacturing installation of the present embodiment is characterised in that, reaction chamber 201 is connected via a plurality of little vent valves 209 with APC valve 210 (exhaust pipe arrangement 208).In this figure, show the example that 12 vent valves 409 are connected in parallel.These 12 vent valves 409 are the structure all simultaneously opening and closing, but are not limited thereto.In addition, similarly to Example 2, the material of transmission window 204 is synthetic quartz, shows the structure that partition is set to the size that can maintain physical strength, in order to eliminate the impact of the shading light part of hog frame 215, be made as the structure that can make sample pedestal 202 work in 2 dimension directions.
In the present embodiment too, use Xe
2excimer lamp (wavelength=172nm) has carried out film forming as VUV lamp 205, use organosilicon source OMCTS as unstripped gas.The wall of reaction chamber 201 and transmission window 204 are set as 120 ℃, and the Temperature Setting of sample pedestal 202 is 30 ℃.At this, although the temperature of the wall of reaction chamber 201 and transmission window 204 is made as to 120 ℃, in guaranteeing the stable on heating scope of O RunddichtringO, establish to such an extent that be highlyer certainly also fine.In addition, the method of heating transmission window 204, has method transmission window 204 directly being heated by thin heater wire and the method that hog frame 215 is heated etc., in the present embodiment, hog frame 215 is heated, by its thermal conduction, transmission window 204 is carried out to indirect heating.
The manufacture method of the optical cvd film of the present embodiment is described below.Technical process during film forming, according to the method shown in Fig. 6.First, after glass substrate 203 is transported to reaction chamber 201, to carrying out vacuum exhaust in reaction chamber 201.Then, all vent valves of exhaust side (in this figure mark 12) are closed, open gas simultaneously and import valve 206 OMCTS is imported to reaction chamber 201.The pressure of reaction chamber 201 moves about sample substrate 202 after starting to rise.The pressure (for example 70Pa) that has reached regulation at the pressure of the pressure transmitter (P1) 207 of reaction chamber afterwards, is closed unstripped gas and is imported valve 206, lights VUV lamp 205.After having passed through specific time, extinguish VUV lamp 205, open vent valve 209 completely, reaction chamber 201 is carried out to vacuum exhaust simultaneously.By repeatedly above operation (sequence), form the optical cvd film of desirable thickness.
So, the manufacturing installation of the optical cvd film of the present embodiment is characterised in that to have: the reaction chamber (201) that substrate is set; Light source portion (vacuum UV lamp 205) from the external irradiation light of reaction chamber; Make described light to the transmission window (204) of reaction chamber transmission; The 1st gas to the unstripped gas of reaction chamber lead-in light cvd film imports valve (206); Be connected a plurality of the 1st vent valves (209) that reaction chamber carried out to exhaust with reaction chamber; Be connected with reaction chamber with via a plurality of the 1st vent valves and the 2nd vent valve (210) that diameter is larger than the diameter of a plurality of the 1st vent valves.
By this feature, the manufacturing installation of the optical cvd film of the present embodiment also plays the effect same with the manufacturing installation of embodiment 2.That is to say, because the film uniformity of formed optical cvd film does not depend on the importing position of unstripped gas completely, the degree of freedom therefore with the setting position of gas trap becomes large and film uniformity and puies forward advantages of higher tremendously.
And, compare with embodiment 2, by configuring pipe arrangement and the valve that a plurality of diameters are little, can realize little conductivity simultaneously and suppress foreign matter producing.In addition, because vent valve is little so can carry out high speed on-off action, in film of the present invention, also can make the ratio of film formation time of essence larger.At this, comparison diagram 2 and Fig. 6 illustrate the different of embodiment 2 and 3 manufacturing installation.The speed that stops and starting that is not both gas exhaust of Fig. 2 and Fig. 6 different.Fig. 2 is the method that the opening and closing speed of gas exhaust valve is slowly carried out, and Fig. 6 makes opening and closing speed method rapidly.As mentioned above, the manufacturing installation of the optical cvd film of the present embodiment, as the conductive method that reduces exhaust system, adopts the structure that increases exhaust-duct.So, by reducing the diameter of 1 exhaust pipe arrangement and using a plurality of pipe arrangements, can reduce the total conc of exhaust pipe arrangement.If exhaust pipe arrangement is little, can use little diaphragm valve, so the manufacturing installation of the optical cvd film of the present embodiment, even if carry out on-off action at a high speed, also can further suppress the generation of foreign matter.In addition, in the application to atom shape CVD device (ALD-CVD method), empirical tests repeatedly open and close the reliability of the little diaphragm valve of processing.Thus, as the combination of vent valve, as a plurality of the 1st vent valves, can use and can suppress the diaphragm valve that foreign matter produces, as the 2nd vent valve, can use APC valve.
In addition, in the present embodiment, the switching of a plurality of vent valves 209 is all carried out simultaneously, but also can be made the switching of each valve regularly stagger slightly, pressure can sharply not changed.In addition, in Fig. 5, show 2 unstripped gases and import valve 206, but in fact unstripped gas importing valve 206 can exist a plurality of.Equally, gas exhaust valve 209 also can exist a plurality of.
Claims (10)
1. a manufacture method for optical cvd film, is characterized in that, comprising:
Operation (a), imports the unstripped gas of described optical cvd film to the reaction chamber that forms optical cvd film, make described reaction chamber reach specified pressure;
Operation (b), in described operation (a) afterwards, stops described unstripped gas, to the importing of described reaction chamber and described unstripped gas from the exhaust of described reaction chamber, to described reaction chamber, irradiating light; With
Operation (c), in described operation (b) afterwards, stops described irradiation, then described reaction chamber is carried out to exhaust,
By described operation (a)～described operation, (c) is repeated multiple times.
2. the manufacture method of optical cvd film according to claim 1, is characterized in that,
Described specified pressure in described operation (a) is less than the pressure of the film forming speed maximum that makes described optical cvd film.
3. a manufacturing installation for optical cvd film, is characterized in that, has:
The reaction chamber of substrate is set;
Light source portion from the external irradiation light of described reaction chamber;
Make described light to the transmission window of described reaction chamber transmission;
The 1st gas imports valve, and it imports the unstripped gas of described optical cvd film to described reaction chamber;
The 1st vent valve, it is connected with described reaction chamber, and described reaction chamber is carried out to exhaust; With
The 2nd vent valve, it is connected with described reaction chamber via described the 1st vent valve, and described reaction chamber is carried out to exhaust.
4. the manufacturing installation of optical cvd film according to claim 3, is characterized in that,
Region between described the 1st vent valve and described the 2nd vent valve also has the 2nd gas importing valve that imports nitrogen.
5. the manufacturing installation of optical cvd film according to claim 4, is characterized in that, also has:
Measure the 1st pressure transmitter of the pressure of described reaction chamber; With
Measure the 2nd pressure transmitter of the pressure in the region between described the 1st vent valve and described the 2nd vent valve,
Described the 2nd gas imports valve and imports described nitrogen, so that the measured value of described the 2nd pressure transmitter equates with the measured value of described the 1st pressure transmitter.
6. the manufacturing installation of optical cvd film according to claim 3, is characterized in that,
The 1st pressure transmitter also with the pressure of measuring described reaction chamber,
Described the 2nd vent valve is by controlling from the signal of described the 1st pressure transmitter.
7. the manufacturing installation of optical cvd film according to claim 3, is characterized in that,
Described the 1st vent valve and described the 2nd vent valve are APC valves.
8. the manufacturing installation of optical cvd film according to claim 3, is characterized in that,
Described the 1st gas imports valve along the arranged transversely of described substrate.
9. a manufacturing installation for optical cvd film, is characterized in that, has:
The reaction chamber of substrate is set;
Light source portion from the external irradiation light of described reaction chamber;
Make described light to the transmission window of described reaction chamber transmission;
The 1st gas imports valve, and it imports the unstripped gas of described optical cvd film to described reaction chamber;
A plurality of the 1st vent valves, it is connected with described reaction chamber, and described reaction chamber is carried out to exhaust; With
The 2nd vent valve, it is connected with described reaction chamber via described a plurality of the 1st vent valves, and diameter is larger than the diameter of described a plurality of the 1st vent valves.
10. the manufacturing installation of optical cvd film according to claim 9, is characterized in that,
Described a plurality of the 1st vent valve is diaphragm valve,
Described the 2nd vent valve is APC valve.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012167922A JP2014027191A (en) | 2012-07-30 | 2012-07-30 | Manufacturing method of photo-cvd film and manufacturing apparatus of photo-cvd film |
| JP2012-167922 | 2012-07-30 |
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| CN103572262A true CN103572262A (en) | 2014-02-12 |
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| CN201310323455.2A Pending CN103572262A (en) | 2012-07-30 | 2013-07-25 | Light CVD film manufacturing method and light CVD film manufacturing apparatus |
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| Country | Link |
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| JP (1) | JP2014027191A (en) |
| KR (1) | KR20140016198A (en) |
| CN (1) | CN103572262A (en) |
| TW (1) | TW201404926A (en) |
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| CN106715752B (en) | 2014-09-19 | 2020-03-20 | 凸版印刷株式会社 | Film forming apparatus and film forming method |
| JP6547271B2 (en) * | 2014-10-14 | 2019-07-24 | 凸版印刷株式会社 | Deposition method by vapor deposition on flexible substrate |
| JP6672595B2 (en) | 2015-03-17 | 2020-03-25 | 凸版印刷株式会社 | Film forming equipment |
| JP7175210B2 (en) | 2019-02-04 | 2022-11-18 | 東京エレクトロン株式会社 | Exhaust device, treatment system and treatment method |
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|---|---|---|---|---|
| EP0653501B1 (en) * | 1993-11-11 | 1998-02-04 | Nissin Electric Company, Limited | Plasma-CVD method and apparatus |
| US20050186789A1 (en) * | 2000-12-07 | 2005-08-25 | Agarwal Vishnu K. | Photo-assisted method for semiconductor fabrication |
| US20100159122A1 (en) * | 2008-12-19 | 2010-06-24 | Canon Kabushiki Kaisha | Deposition film forming apparatus, deposition film forming method and electrophotographic photosensitive member manufacturing method |
| US20110230061A1 (en) * | 2008-09-03 | 2011-09-22 | Hitachi Koskusai Electric Inc. | Manufacturing method of semiconductor device |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6212121A (en) * | 1985-07-10 | 1987-01-21 | Hitachi Ltd | Photo processing equipment |
| JPS63232416A (en) * | 1987-03-20 | 1988-09-28 | Sony Corp | Formation of thin-film through photochemical vapor growth |
| JPH04302138A (en) * | 1991-03-29 | 1992-10-26 | Furukawa Electric Co Ltd:The | Vapor growth device for semiconductor wafer |
| JPH04329626A (en) * | 1991-05-02 | 1992-11-18 | Matsushita Electron Corp | Processor of semiconductor device |
| JPH05251362A (en) * | 1992-03-06 | 1993-09-28 | Fujitsu Ltd | Low-pressure treatment device |
| JPH1011152A (en) * | 1996-06-26 | 1998-01-16 | Dainippon Screen Mfg Co Ltd | Vacuum exhaustion device of processor |
| JP2001060578A (en) * | 1999-08-20 | 2001-03-06 | Nec Corp | Vacuum treatment apparatus |
| JP4644242B2 (en) * | 2007-12-10 | 2011-03-02 | 忠弘 大見 | How to use vacuum exhaust valve |
-
2012
- 2012-07-30 JP JP2012167922A patent/JP2014027191A/en active Pending
-
2013
- 2013-06-19 TW TW102121717A patent/TW201404926A/en unknown
- 2013-07-25 CN CN201310323455.2A patent/CN103572262A/en active Pending
- 2013-07-29 KR KR1020130089855A patent/KR20140016198A/en not_active Application Discontinuation
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0653501B1 (en) * | 1993-11-11 | 1998-02-04 | Nissin Electric Company, Limited | Plasma-CVD method and apparatus |
| US20050186789A1 (en) * | 2000-12-07 | 2005-08-25 | Agarwal Vishnu K. | Photo-assisted method for semiconductor fabrication |
| US20110230061A1 (en) * | 2008-09-03 | 2011-09-22 | Hitachi Koskusai Electric Inc. | Manufacturing method of semiconductor device |
| US20100159122A1 (en) * | 2008-12-19 | 2010-06-24 | Canon Kabushiki Kaisha | Deposition film forming apparatus, deposition film forming method and electrophotographic photosensitive member manufacturing method |
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| KR20140016198A (en) | 2014-02-07 |
| JP2014027191A (en) | 2014-02-06 |
| TW201404926A (en) | 2014-02-01 |
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Application publication date: 20140212 |