CN102312191B - Magnetically controlled DC sputtering is utilized to prepare the method for high resistance transparent ZnO film - Google Patents
Magnetically controlled DC sputtering is utilized to prepare the method for high resistance transparent ZnO film Download PDFInfo
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Abstract
The present invention relates to a kind of method utilizing magnetically controlled DC sputtering to prepare high resistance transparent ZnO film, it is characterized in that based on rich Zn (or scarce O
2) zinc-oxide-base wide-bandgap stupalith target, utilize magnetically controlled DC sputtering to instead of traditional rf magnetron sputtering and prepare high resistant zno-based transparent film, for thin-film solar cells diffusion impervious layer and Window layer.By adjusting process parameter, the resistivity of the Zinc oxide-base high resistance transparent film of preparation can be controlled in 10
4~ 10
8in the scope of Ω cm, at visible and near-infrared region average transmittances about 90%, compared with the high resistant ZnO film prepared based on commercial intrinsic ZnO ceramic target radio-frequency magnetron sputter method, under identical thickness condition, the film transmission rate of preparation, resistivity and surfaceness are suitable with it.Preparation technology of the present invention is simple, with low cost, and has visible and that near-infrared region is high transparency, can be widely used in transparent electron and Novel Optoelectronic Device field especially thin-film solar cells.
Description
Technical field
The present invention relates to a kind of preparation method utilizing magnetically controlled DC sputtering to prepare high resistance transparent zno-based film.Belong to transparent conductive film material (TCM) technical field.
Background technology
High resistance transparent ZnO film has a wide range of applications in transparent electron and Novel Optoelectronic Device field, in thin-film solar cells and photoelectric device, resistance within the specific limits ZnO film that is controlled, high permeability can be used as Window layer and diffusion impervious layer, can improve homogeneity and the stability of hull cell especially significantly.In non-crystalline silicon, microcrystal silicon and CdTe thin film solar cell, skim high resistance transparent ZnO film is deposited between back electrode and N-type light absorbing zone, can be used as diffusion impervious layer [(1) A.V.Shah, H.Schade, et al.Progress in Photovoltaics:Research and Applications, 12 (2004) 113; (2) B.Rech, B.Wieder, C.Beneking, et al.26
thiEEE PVSpecialists Conf [C], 1997:619-622], electrode atom and the phase mutual diffusion of light absorbing zone atom in interface can be prevented on the one hand, the thickness of Window layer electrode can be reduced on the other hand, thus raising transmitance, also effectively can reduce the dark current of battery, improve its shunting resistance, improve open circuit voltage.Copper-indium-galliun-selenium (CIGS) solar battery window layer ZnO film is made up of high resistant ZnO (intrinsic ZnO or i-ZnO) and low-resistance ZnO (ZnO:Al or n-ZnO), high resistant i-ZnO layer mainly contains two effects in CIGS solar cell, one is the internal short-circuit reducing battery, film copper indium gallium selenium solar cell causes current loss due to ohmic contact between the electrode of front and back, and high resistant zinc oxide film can eliminate the front and back electric pole short circuit because surface hole or surface distress cause; Another effect is exactly that the band edge of enable band mates more.
The raising of high resistance transparent ZnO to battery efficiency has important effect.For film copper indium gallium selenium solar cell, the detailed research i-ZnO of Karin Ottosson is on the impact [(3) K.Ottosson, UPTEC F06 001, Examensarbete 20p, April 2006] of CIGS battery performance.Find the i-ZnO layer of sputtering 70 ~ 100nm, effectively can eliminate the short circuit phenomenon that battery device easily occurs, the efficiency about 2% of battery can be improved, mainly improve open circuit voltage and the packing factor of battery.The hot carrier produced due to the absorption of i-ZnO layer to light is not contributed battery circuit (from the quantum yield curve of battery, therefore, should reduce the absorption of i-ZnO layer to light as far as possible.I-ZnO layer should have suitable resistivity simultaneously, and resistivity is too low, and the probability of internal short-circuit of battery is just large, and the performance of battery will decline; But the too high meeting of resistivity causes the potential barrier of electron tunneling too high, makes the internal resistance of cell too high, photoelectric transformation efficiency declines.In general, the resistivity of high resistant i-ZnO layer should 10
4~ 10
8in the scope of Ω cm, transmitance should about 90%, and thickness should be proper between 60 ~ 120nm.
The method preparing high resistance transparent ZnO film at present has a lot: [(4) Y.J.Kim such as magnetron sputtering, pulsed light deposition (PLD), atomic layer epitaxy (ALE), gas phase epitaxy of metal organic compound (MOCVD), molecular beam epitaxy (MBE), C.H.Lee, et al.Appl.Phys.Lett.89 (2006) 163128; (5) X.N.Li, A.E.Sally, et al.J.Vac.Sci.Technol.A 24 (2006) 1213; (6) S.W.Kim, S.Z.Fujita, et al.Appl.Phys.Lett.88 (2006) 253114], wherein sputtering sedimentation is making ZnO film one of utilisation technology the most widely.For conventional magnetron sputtering method, general employing intrinsic ZnO ceramic target, because intrinsic ZnO is wide bandgap semiconductor (3.3eV), commercial ceramic target electroconductibility is very poor and substantially close to state of insulation, thus traditional preparation methods all adopts radio-frequency magnetron sputter method [(7) J.Ch.Lee, K.H.Kang, etc.Solar Energy Materials & Solar Cells 64 (2000) 185].And industry member is got on very well, because radio-frequency power supply is expensive and be difficult to be used on a large scale.Comparatively speaking; in large-scale industrial is produced; direct supply platform has higher process consistency and controlling functions; single with regard to window layer material; if high resistant ZnO (i-ZnO) and low-resistance window electrode can adopt magnetically controlled DC sputtering; then not only can reduce costs, also can greatly reduce technique change, and then improve output.But as previously described, general commercial ZnO ceramic target, because of its high resistance, uses direct supply almost cannot build-up of luminance, is thus difficult to use magnetically controlled DC sputtering technology.
Based on this factor, there is investigator to attempt to utilize ZnO:Al (AZO) to conduct electricity target, adopt direct supply at high O
2sputter under the condition of dividing potential drop to prepare high resistant ZnO film [(8) W.N.Shafarman, R.Klenk, etc.J.Appl.Phys.79 (1996) 7324; (9) J.Hedstrom, H.Ohlsen, etc.Conf.Rec.23rd IEEE Photovolt.Spec.Conf.IEEE, Piscataway, N.J., 364 (1993); (10) W.E.Devaney, W.S.Chen, etc.IEEE Trans.Electron Dev.37 (1990) 428; (11) M.Kemell, M.Ritala, etc.Critical Reviews in Solid State and Materials Sciences, 30 (2005) 1-31].In the environment of oxygen enrichment, high oxygen partial pressure can stop the formation of Lacking oxygen, thus reduces the electroconductibility of ZnO film.But oxygen level too high in plasma body can cause damage [(12) T.Nakada, M.Mizutani, Jpn.J.Appl.Phys.41 (2002) L165 of the preposition film of internal layer; (13) K.Kushiya, T.Nii, etc.Jpn.J.Appl.Phys.35 (1996) 4383], thus affect the performance of solar cell, also there is complex process, high in cost of production problem simultaneously, be difficult to be applicable to large-scale production.
In sum, develop a kind of novel process and prepare high resistance transparent zno-based film, be expected to be with a wide range of applications in transparent electron and Novel Optoelectronic Device field, be especially of great immediate significance in the Application Areas of thin-film solar cells, its research and development face serious urgency.
Summary of the invention
The object of the invention is to provide a kind of method utilizing direct current magnetron sputtering process to prepare high-performance N-type high resistance transparent zno-based film.The design of invention is: adopt liquid phase method co-precipitation to prepare the ZnO nano powder of high sintering activity, utilizes this nano-powder carrying out ultrahigh relative density sintering by unique sintering process lower than 900 DEG C for raw material, obtains rich Zn (or the scarce O of high-compactness
2) ZnO target (separate case application); On this basis, utilize high vacuum magnetron sputtering technique, the high resistance transparent zno-based film prepared by magnetically controlled DC sputtering, can be applicable to copper-indium-galliun-selenium film solar cell Window layer.This rich Zn (or the scarce O utilizing preparation
2) ZnO film prepared by zinc oxide ceramic target magnetically controlled DC sputtering, at visible ray until near-infrared region (400 ~ 2200nm) average transmittances is all about 90%, the resistivity of thickness i-ZnO layer when 80nm is 10
4~ 10
8controlled in the scope of Ω cm, meet the application requiring of thin-film solar cells Window layer and diffusion impervious layer and other photoelectric device.Compared with the high resistant ZnO film prepared based on commercial intrinsic ZnO ceramic target radio-frequency magnetron sputter method, under identical thickness condition, film transmission rate, resistivity and surfaceness prepared by the present invention are suitable with it.
The present invention is described below in detail.
A) film preparation
The present invention adopts rich Zn (or scarce O
2) the general structure of ZnO target be Zn
1+xo or ZnO
1-x0.05 < X≤0.2 (applying for separately), adopt direct current magnetron sputtering process (and unconventional radio-frequency magnetron sputter method) to prepare N-shaped high resistance transparent zno-based film, be applied to transparent electron and Novel Optoelectronic Device field.The concrete preparation technology of film is: adopt rich Zn (or scarce O
2) ZnO target, utilize magnetically controlled DC sputtering, with simple glass, quartz or organic flexible material for substrate, base vacuum is evacuated to 1.0 ~ 3.0 × 10
-4pa, with rare gas element, especially the mixed gas of high-purity argon gas and oxygen is working gas (O
2the volume percent accounting for total tolerance controls be greater than 0 ~ 1.5%), operating air pressure maintains 0.5 ~ 3Pa, and the distance between substrate and target is 5 ~ 10cm; Magnetron sputtering power is 40 ~ 120W; The sputtering sedimentation time is 2 ~ 15min; The thickness of the film of preparation is 60 ~ 800nm.Can as required, by the thickness and the quality that regulate the distance etc. of sputtering time, sputtering power, operating air pressure and target and substrate to control film.The power of the magnetron sputtering of preferential recommendation is 70-80W, and the distance between substrate and target is 7-8cm.In described high-purity argon, the percent by volume of argon gas is >=99.9%.
B) sample characterization and performance evaluation
1., the thing phase of film and morphology characterization
To gained film sample of the present invention by scanning electron microscopic observation film surface appearance, Electronic Speculum model used is LEO-1530VP; The surfaceness of viewing film is carried out by atomic force microscope (AFM, Japanese Seiko II SPI3800V & spa300HV type); The thickness of measure sample is carried out by Dektak150 type surface profiler; By X-ray powder diffractometer (Rigaku D/Max-2550V) analysed film thing phase.
2., optical property characterizes
The transmitance of film ultraviolet-visible-near infrared spectrometer (HITACHIUV-3010PC) testing film that the present invention is obtained.
3., electric property characterizes
After gained film sample point silver electrode of the present invention, Hall effect is utilized to adopt vanderburg four probe method (Accent HL5500 Hall instrument) to carry out conductivity evaluation.
Accompanying drawing explanation
The transmitted light spectrogram of the thick ZnO film sample of 800nm prepared by Fig. 1 d.c. sputtering and radio-frequency sputtering;
The X-ray diffractogram of the thick ZnO film sample of 800nm prepared by Fig. 2 d.c. sputtering and radio-frequency sputtering;
The surface topography AFM of the thick ZnO film sample of 800nm prepared by Fig. 3 d.c. sputtering and radio-frequency sputtering schemes;
The surfaceness (RMS) of the thick ZnO film sample of 800nm prepared by Fig. 4 d.c. sputtering and radio-frequency sputtering;
The transmitted light spectrogram of the thick ZnO film sample of 80nm prepared by Fig. 5 d.c. sputtering;
The X-ray diffractogram of the thick ZnO film sample of 80nm and 800nm prepared by Fig. 6 d.c. sputtering.
Embodiment
Introduce embodiments of the invention below, to increase further understanding of the present invention, but the present invention is limited to embodiment absolutely not.
Embodiment 1:
Adopt rich Zn (or scarce O
2) ZnO target (separate case application), utilize magnetically controlled DC sputtering, take simple glass as substrate, base vacuum is evacuated to 2.0 × 10
-4pa, take high-purity argon gas as working gas, passes into a small amount of O in addition
2(O
2the volume percent accounting for total gas couette is 0.5%), operating air pressure maintains 1.2Pa, and target and substrate distance are set to 7cm, and sputtering power is 80W, and depositing time is 40min.In addition, for the purpose of contrast, adopt commercial intrinsic ZnO ceramic target, with radio-frequency magnetron sputter method, under identical base vacuum, atmosphere, air pressure and range condition, sputter 60min.Film sample thickness obtained under two kinds of conditions is 800nm.
Fig. 1 is the transmitted spectrum of the ZnO film sample prepared under two kinds of conditions, and can see, film reaches more than 90% at the average transmittances of visible region, even if to near-infrared region (2200nm), still keep the transmitance of 90% nearly.Fig. 2 is the X-ray diffractogram of the ZnO film sample prepared under two kinds of conditions.From result in figure, obtained ZnO film is (002) crystal orientation preferential growth, and film obtained by d.c. sputtering shows stronger crystallinity.Result shows, under identical thickness condition, the ZnO film that the present invention utilizes direct current magnetron sputtering process to prepare has prepares the suitable very high visible and near-infrared band transmitance of film with radio-frequency sputtering, and shows stronger crystallinity.
Fig. 3, Fig. 4 are that the surface topography AFM of the ZnO film sample prepared under two kinds of conditions schemes.Can be found out by surfaceness (RMS) result of Fig. 4, under identical thickness condition, the high resistant ZnO film (RMS:27.6nm) that the present invention utilizes direct current magnetron sputtering process to prepare has prepares the suitable surfaceness of film (RMS:25.8nm) with radio-frequency sputtering.
Embodiment 2:
In the application of thin-film solar cells and field of photoelectric devices, the thickness general control of high resistant ZnO film is between 60 ~ 120nm.The present embodiment adopts the sintering temperature of 850 DEG C to sinter 20 hours, obtained rich zinc state Zn
1.13the broad stopband stupalith target of O structure, utilize magnetically controlled DC sputtering, take simple glass as substrate, base vacuum is evacuated to 2.0 × 10
-4pa, take high-purity argon gas as working gas, passes into a small amount of O in addition
2(O
2account for 0.5% of total gas couette), operating air pressure maintains 1.2Pa, and target and substrate distance are set to 7cm, and sputtering power is 80W, and depositing time is 4min.Obtained film sample thickness is 80nm.
Fig. 5 is the transmitted spectrum of ZnO film sample of preparation, can see, film reaches 90% nearly, even if to near-infrared region (2200nm), still keep the transmitance of 90% at the average transmittances of visible region.Fig. 6 is the X-ray diffractogram of the thick sample of 800nm prepared under the ZnO film sample condition in the same manner as in Example 1 of preparation.Result shows, the thick ZnO film of obtained 80nm has presented certain crystallinity, is (002) crystal orientation preferential growth.The test result of electrical property shows, obtained thickness of sample resistivity about 6 × 10 when 80nm under this implementation condition
6Ω cm, meets the application requiring of CIGS (copper indium gallium tin) thin-film solar cells Window layer and diffusion impervious layer and other photoelectric device.
Embodiment 3:
Adopt rich Zn (or scarce O
2) ZnO target, utilize magnetically controlled DC sputtering, take simple glass as substrate, base vacuum is evacuated to 2.0 × 10
-4pa, with pure high-purity argon gas for working gas, operating air pressure maintains 1.2Pa, and target and substrate distance are set to 7cm, and sputtering power is 80W, and depositing time is 4min.Obtained film sample thickness is 80nm.The test result of electrical property shows, obtained sample resistivity about 7 × 10 under the condition of the present embodiment
5Ω cm, slightly lower than embodiment 2, at visible ray until near-infrared region (400 ~ 2200nm) average transmittances is all about 90%, suitable with embodiment 2, meet the application requiring of thin-film solar cells Window layer and diffusion impervious layer and other photoelectric device.
Embodiment 4:
Adopt rich Zn (or scarce O
2) ZnO target, utilize magnetically controlled DC sputtering, take silica glass as substrate, base vacuum is evacuated to 2.0 × 10
-4pa, take high-purity argon gas as working gas, passes into a small amount of O in addition
2(O
2account for 1.0% of total gas couette), operating air pressure maintains 0.8Pa, and target and substrate distance are set to 9cm, and sputtering power is 50W, and depositing time is 12min.Obtained film sample thickness is about 100nm.The test result of electrical property shows, obtained sample resistivity about 8 × 10 under this implementation condition
6Ω cm, a little more than embodiment 2, at visible ray until near-infrared region (400 ~ 2200nm) average transmittances is all about 90%, suitable with embodiment 2, meet the application requiring of thin-film solar cells Window layer and diffusion impervious layer and other photoelectric device.
Embodiment 5:
Adopt rich Zn (or scarce O
2) ZnO target, utilize magnetically controlled DC sputtering, take simple glass as substrate, base vacuum is evacuated to 2.0 × 10
-4pa, take high-purity argon gas as working gas, passes into a small amount of O in addition
2(O
2account for 0.3% of total gas couette), operating air pressure maintains 0.5Pa, and target and substrate distance are set to 10cm, and sputtering power is 120W, and depositing time is 2min.Obtained film sample thickness is about 60nm.The test result of electrical property shows, obtained sample resistivity about 3.4 × 10 under this implementation condition
4Ω cm, lower than embodiment 2, at visible ray until near-infrared region (400 ~ 2200nm) average transmittances is higher than 90%, a little more than embodiment 2, meets the application requiring of thin-film solar cells Window layer and diffusion impervious layer and other photoelectric device.
Embodiment 6:
Adopt rich Zn (or scarce O
2) ZnO target, utilize magnetically controlled DC sputtering, with organic flexible material polyimide (PI) for substrate, base vacuum is evacuated to 2.0 × 10
-4pa, take high-purity argon gas as working gas, passes into a small amount of O in addition
2(O
2account for 1.5% of total gas couette), operating air pressure maintains 3.0Pa, and target and substrate distance are set to 8cm, and sputtering power is 100W, and depositing time is 5min.Obtained film sample thickness is about 70nm.The test result of electrical property shows, obtained sample resistivity about 6 × 10 under this implementation condition
7Ω cm, higher than embodiment 2, at visible ray until near-infrared region (400 ~ 2200nm) average transmittances is all about 90%, a little less than embodiment 2, meets the application requiring of thin-film solar cells Window layer and diffusion impervious layer and other photoelectric device.
Embodiment 7:
Adopt homemade rich Zn (or scarce O
2) ZnO target, utilize magnetically controlled DC sputtering, take simple glass as substrate, base vacuum is evacuated to 2.0 × 10
-4pa, take high-purity argon gas as working gas, passes into a small amount of O in addition
2(O
2account for 0.3% of total gas couette), operating air pressure maintains 2.0Pa, and target and substrate distance are set to 5cm, and sputtering power is 40W, and depositing time is 8min.Obtained film sample thickness is about 100nm.The test result of electrical property shows, obtained sample resistivity about 6 × 10 under this implementation condition
6Ω cm, suitable with embodiment 2, at visible ray until near-infrared region (400 ~ 2200nm) average transmittances is all about 90%, suitable with embodiment 2, meet the application requiring of thin-film solar cells Window layer and diffusion impervious layer and other photoelectric device.
Embodiment 8:
Adopt homemade rich Zn (or scarce O
2) ZnO target, utilize magnetically controlled DC sputtering, take simple glass as substrate, base vacuum is evacuated to 2.0 × 10
-4pa, take high-purity argon gas as working gas, passes into a small amount of O in addition
2(O
2account for 0.3% of total gas couette), operating air pressure maintains 2.0Pa, and target and substrate distance are set to 7cm, and sputtering power is 80W, and depositing time is 5min.Obtained film sample thickness is about 100nm.The test result of electrical property shows, obtained sample resistivity about 7.5 × 10 under this implementation condition
7Ω cm, higher than embodiment 2, at visible ray until near-infrared region (400 ~ 2200nm) average transmittances is all about 90%, suitable with embodiment 2, meet the application requiring of thin-film solar cells Window layer and diffusion impervious layer and other photoelectric device.
Embodiment 9:
Adopt homemade rich Zn (or scarce O
2) ZnO target, utilize magnetically controlled DC sputtering, take simple glass as substrate, base vacuum is evacuated to 2.0 × 10
-4pa, take high-purity argon gas as working gas, passes into a small amount of O in addition
2(O
2account for 0.3% of total gas couette), operating air pressure maintains 0.5Pa, and target and substrate distance are set to 9cm, and sputtering power is 60W, and depositing time is 8min.Obtained film sample thickness is about 120nm.The test result of electrical property shows, obtained sample resistivity about 7.2 × 10 under this implementation condition
6Ω cm, a little more than embodiment 2, at visible ray until near-infrared region (400 ~ 2200nm) average transmittances about about 90%, a little less than embodiment 2, meets the application requiring of thin-film solar cells Window layer and diffusion impervious layer and other photoelectric device.
Structural formula described in above embodiment 1-9 is Zn
1+xo or ZnO
1-x, 0.05 < X≤0.2 ceramic target is that the preparation of the zinc oxide of rich zinc or anoxic comprises the following steps:
A) prepared burden according to mol ratio in zinc source and oxygen source, then obtain the nano-ZnO precursor powder of high reactivity, high crystalline through mixing, oven dry and grinding;
B) step a prepare by high performance precursor powder granulation, by the moulded section of isostatic pressed means, prepare the biscuit of ceramics of high compacted density;
C) adopt upper and lower two crucibles, in lower crucible, sink to graphite, in upper crucible, insert ZnO biscuit of ceramics that step b suppresses and be inverted on lower crucible; Adopt and sinter less than or equal under the sintering temperature of 900 DEG C, obtained described rich Zn or scarce O
2zinc-oxide-base wide-bandgap stupalith target;
Described zinc source be selected from metallic zinc, zinc oxide, zinc acetate, zinc oxalate, zinc citrate, zinc nitrate, zinc sulfate, zinc fluoride and zinc chloride one or more;
Describedly containing oxygen source be: one or more in ammoniacal liquor, sodium hydroxide, potassium hydroxide, urea, thiocarbamide and hydrazine.
The sintering temperature that step c adopts is 500-900 DEG C.
Under described sintering temperature, sintering time is 2-24 hour.
Claims (6)
1. utilize magnetically controlled DC sputtering to prepare a method for high resistance transparent ZnO film, it is characterized in that:
(1) utilize the zno-based target of rich zinc or anoxic, with simple glass, silica glass or organic flexible material for substrate, controlling background vacuum is 1.0 × 10
-4-3.0 × 10
-4pa;
(2) with the mixed gas of rare gas element and oxygen for working gas, by controlling the power of magnetron sputtering, time, the pressure of working gas and the distance between target and substrate, prepare the ZnO film of N-shaped high resistance transparent to substitute the technique of traditional rf magnetron sputtering;
The structural formula of described rich zinc or the zno-based target of anoxic is Zn
1+xo or ZnO
1-x, 0.05 < X≤0.2 in formula;
In described working gas, oxygen accounts for the volume percent of total tolerance is 0.3-1.5%;
Distance between described target and substrate is 5-10cm;
The power of described magnetron sputtering is 40-120w,
The described sputtering sedimentation time is 2-15min, and the pressure of described working gas is 0.5-3Pa.
2., by method according to claim 1, it is characterized in that described rare gas element is high-purity argon, the percent by volume of argon gas is >=99.9%.
3., by method according to claim 1, it is characterized in that the distance between target and substrate is 7-8cm.
4., by method according to claim 1, it is characterized in that described sputtering power is 70-80W.
5., by the method described in claim 1 or 4, it is characterized in that the resistivity of the N-shaped high resistant zinc-oxide film prepared is 10
4-10
8Ω cm.
6., by the method described in claim 1 or 4, it is characterized in that the thickness of the N-shaped high resistant zinc-oxide film prepared is 60-80nm, and at (002) crystal orientation preferential growth.
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| WO2013109588A1 (en) * | 2012-01-20 | 2013-07-25 | Caterpillar Inc. | Zinc oxide sulfur sensors and methods of manufacture thereof |
| TWI480953B (en) * | 2012-03-30 | 2015-04-11 | Hannstouch Solution Inc | Composite transparent oxide film and manufacturing method for the same |
| CN103866232B (en) * | 2014-03-06 | 2016-04-27 | 上海理工大学 | A kind of preparation method of buffer layer of the copper-indium-galliun-selenium film solar cell without cadmium |
| CN108285278B (en) * | 2017-12-21 | 2020-09-15 | 凯盛科技股份有限公司 | Preparation method of high-resistance and high-transmittance ITO glass substrate |
| CN110444402B (en) * | 2019-07-09 | 2020-09-25 | 淮阴工学院 | BiVO (BiVO-enhanced)4Method for photoelectrochemical property of photoanode |
| CN111996508A (en) * | 2020-08-27 | 2020-11-27 | 苏州黑星科技有限公司 | Preparation method of amorphous silicon photoelectric layer film based on photoelectric tweezers equipment |
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| JPH05279716A (en) * | 1992-04-01 | 1993-10-26 | Sumitomo Metal Ind Ltd | Method for charging material to be charged into blast furnace |
| EP1081256A2 (en) * | 1999-08-31 | 2001-03-07 | Stanley Electric Co., Ltd. | ZnO crystal growth method, ZnO crystal structure, and semiconductor device using ZnO crystal |
| CN101283122A (en) * | 2005-08-09 | 2008-10-08 | 斯坦雷电气株式会社 | ZnO crystal, method for growing the crystal, and method for manufacture of light-emitting element |
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