CN102312191A - Method for preparing high-resistance transparent zinc oxide (ZnO) thin film by utilizing direct current magnetic control sputtering equipment - Google Patents
Method for preparing high-resistance transparent zinc oxide (ZnO) thin film by utilizing direct current magnetic control sputtering equipment Download PDFInfo
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Abstract
The invention relates to a method for preparing a high-resistance transparent zinc oxide (ZnO) thin film by utilizing direct current magnetic control sputtering equipment, which is characterized in that based on Zn-rich (or O2-inefficient) zinc oxide-based wide bandgap ceramic material target, direct current magnetic control sputtering is utilized to replace traditional radio frequency magnetic control sputtering to prepare the high-resistance ZnO-based transparent thin film, and the transparent thin film is used for the diffusion barrier layers and the window layers of thin film solar cells. Through regulating technological parameters, the resistivity of the prepared high-resistance ZnO-based transparent thin film can be controlled to be within the range of 104-108omega.cm, and the average transmissivity in visual and near infrared zones is about 90 percent. Compared with the high-resistance ZnO-based thin film prepared a radio frequency magnetic control sputtering method based on a commercial intrinsic ZnO ceramic target, under the condition of same film thickness, the transmissivity, the resistivity and the surface toughness are equivalent to those of the thin film prepared by the method of the invention. The high-resistance transparent zinc oxide (ZnO) thin film has a simple preparation process, low cost and high transparency in the visual and near infrared zones, and can be widely applied to the field of transparent electronics and novel photoelectric devices, especially the thin film solar cells.
Description
Technical field
The present invention relates to a kind of preparation method who utilizes magnetically controlled DC sputtering to prepare high resistance transparent zno-based film.Belong to transparent conductive film material (TCM) technical field.
Background technology
The high resistance transparent ZnO film has a wide range of applications at transparent electronics and novel photoelectric devices field; In thin-film solar cells and photoelectric device; Resistance is controlled within the specific limits, the ZnO film of high permeability can be used as Window layer and diffusion impervious layer, can improve the homogeneity and the stability of hull cell especially significantly.In non-crystalline silicon, microcrystal silicon and CdTe thin-film solar cells; Deposition skim high resistance transparent ZnO film 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], can prevent that on the one hand electrode atom and light absorbing zone atom from the interface mutual diffusion mutually, can reduce the thickness of Window layer electrode on the other hand; Thereby raising transmitance; Also can reduce the dark current of battery effectively, improve its shunting resistance, improve open circuit voltage.Copper-indium-galliun-selenium (CIGS) solar battery window layer ZnO film is to be 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 the CIGS solar cell; The one, the internal short-circuit of reduction battery; The film copper indium gallium selenium solar cell since between the electrode of front and back ohmic contact cause current loss, the high resistant zinc oxide film can be eliminated the front and back electric pole short circuit that causes because of surface hole or surface distress; Another effect be exactly enable with band edge mate more.
High resistance transparent ZnO has important effect to the raising of battery efficiency.With the film copper indium gallium selenium solar cell is example, and the detailed research i-ZnO of Karin Ottosson is to the influence of CIGS battery performance [Examensarbete 20p, April 2006 for (3) K.Ottosson, UPTEC F06 001].Find the i-ZnO layer of sputter 70～100nm, can eliminate the short circuit phenomenon that battery device occurs easily effectively, it is about 2% to improve the efficient of battery, mainly is open circuit voltage and the packing factor that has improved battery.Because the i-ZnO layer does not have contribution (can know from the quantum yield curve of battery, therefore, should reduce the absorption of i-ZnO layer to light the hot carrier that absorption produced of light to battery circuit as far as possible.The i-ZnO layer should have suitable resistivity simultaneously, and resistivity is low excessively, and the probability of internal short-circuit of battery is just big, and the performance of battery will descend; But the too high meeting of resistivity causes the potential barrier of electron tunneling too high, makes the internal resistance of cell too high, and photoelectric transformation efficiency descends.In general, the resistivity of high resistant i-ZnO layer should be 10
4～10
8In the scope of Ω cm, transmitance should be about 90%, and thickness should be proper between 60～120nm.
The method for preparing at present the high resistance transparent ZnO film has a lot: magnetron sputtering, pulsed light deposition (PLD), atomic layer epitaxy (ALE), gas phase epitaxy of metal organic compound (MOCVD), molecular beam epitaxy [(4) Y.J.Kim such as (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 preparation ZnO film one of utilisation technology the most widely.For magnetron sputtering method commonly used; The general intrinsic ZnO ceramic target that adopts; Because intrinsic ZnO is wide bandgap semiconductor (3.3eV), commercial ceramic target electroconductibility is very poor and basically near state of insulation, thereby the traditional preparation process method all adopts radio-frequency magnetron sputter method [(7) J.Ch.Lee; K.H.Kang, etc.Solar Energy Materials & Solar Cells 64 (2000) 185].And get on very well for industry member, owing to costing an arm and a leg, radio-frequency power supply is difficult to be able on a large scale use.Comparatively speaking; In large-scale industrial was produced, the direct supply platform has higher process consistency and function, and was single with regard to the Window layer material; If high resistant ZnO (i-ZnO) and low-resistance window electrode can both adopt magnetically controlled DC sputtering; Then not only can reduce cost, also can significantly reduce technique change, and then improve output.Yet as noted earlier, general commercial ZnO ceramic target is because of its high resistance, uses the direct supply almost can't build-up of luminance, thereby is difficult to use the magnetically controlled DC sputtering technology.
Based on this factor, there is the investigator to attempt to utilize ZnO:Al (AZO) conduction target, adopt direct supply at high O
2[etc.J.Appl.Phys.79 (1996) 7324 for (8) W.N.Shafarman, R.Klenk with preparation high resistant ZnO film in sputter under the condition of dividing potential drop; (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 in oxygen room, thereby reduces the electroconductibility of ZnO film.But too high oxygen level can cause damage [(12) T.Nakada, M.Mizutani, Jpn.J.Appl.Phys.41 (2002) L165 of the preposition film of internal layer in the plasma body; (13) K.Kushiya, T.Nii, etc.Jpn.J.Appl.Phys.35 (1996) 4383], thereby influence Solar cell performance, also there are problems such as complex process, cost height 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 at transparent electronics and novel photoelectric devices field, especially the Application Areas in thin-film solar cells is of great immediate significance, and its research and development face serious urgency.
Summary of the invention
The object of the invention is to provide a kind of method of utilizing direct current magnetron sputtering process to prepare high-performance N type high resistance transparent zno-based film.The design of invention is: adopt the active ZnO nano-powder of the high sintering of liquid phase method prepared by co-precipitation, utilize this nano-powder for the sintering process of raw material through uniqueness carries out superelevation density sintering being lower than 900 ℃, obtained rich Zn (or the scarce O of high-compactness
2) ZnO target (separate case application); On this basis, utilize high vacuum magnetic control sputtering technology, the high resistance transparent zno-based film through the magnetically controlled DC sputtering preparation can be applicable to the copper-indium-galliun-selenium film solar cell Window layer.Rich Zn (or the scarce O of this utilization preparation
2) the prepared ZnO film of zinc oxide ceramics target magnetically controlled DC sputtering, (all about 90%, the resistivity of thickness i-ZnO layer when 80nm is 10 for 400～2200nm) average transmittanceies until the near-infrared region at visible light
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.Compare with the high resistant ZnO film for preparing based on commercial intrinsic ZnO ceramic target radio-frequency magnetron sputter method, under identical thickness condition, film transmitance, resistivity and the surfaceness of the present invention's preparation are suitable with it.
Describe the present invention 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-x, 0.05＜X≤0.2 (application separately) adopted direct current magnetron sputtering process (and non-traditional radio-frequency magnetron sputter method) preparation n type high resistance transparent zno-based film, is applied to transparent electronics and novel photoelectric devices field.The concrete preparation technology of film is: adopt rich Zn (or scarce O
2) the ZnO target, utilize magnetically controlled DC sputtering, be substrate with simple glass, quartz or organic flexible materials, 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 that accounts for total tolerance is controlled at 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 wait thickness and the quality of controlling film through the distance of regulating sputtering time, sputtering power, operating air pressure and target and substrate as required.The power of the preferential magnetron sputtering of recommending is 70-80W, and the distance between substrate and target is 7-8cm.In the described high-purity argon, the percent by volume of argon gas is >=99.9%.
B) sample characterization and performance evaluation
1., the thing of film characterizes with pattern
Through the scanning electron microscopic observation film surface appearance, used Electronic Speculum model is LEO-1530VP to gained film sample of the present invention; The surfaceness of coming viewing film through AFM (AFM, Japanese Seiko II SPI3800V & spa300HV type); Come the thickness of measure sample through Dektak150 type surface profiler; Through X-ray powder diffraction appearance (Rigaku D/Max-2550V) analysed film thing phase.
2., optical property characterizes
With the transmitance of the resulting film of the present invention with ultraviolet-visible-near infrared spectrometer (HITACHIUV-3010PC) testing film.
3., electric property characterizes
After gained film sample point silver electrode of the present invention, utilize Hall effect to adopt vanderburg four probe method (Accent HL5500 Hall appearance) to carry out the conductivity evaluation.
Description of drawings
The transmitted light spectrogram of the thick ZnO film sample of 800nm of Fig. 1 d.c. sputtering and radio-frequency sputtering preparation;
The X-ray diffractogram of the thick ZnO film sample of 800nm of Fig. 2 d.c. sputtering and radio-frequency sputtering preparation;
The surface topography AFM figure of the thick ZnO film sample of 800nm of Fig. 3 d.c. sputtering and radio-frequency sputtering preparation;
The surfaceness (RMS) of the thick ZnO film sample of 800nm of Fig. 4 d.c. sputtering and radio-frequency sputtering preparation;
The transmitted light spectrogram of the thick ZnO film sample of 80nm of Fig. 5 d.c. sputtering preparation;
The 80nm of Fig. 6 d.c. sputtering preparation and the X-ray diffractogram of the thick ZnO film sample of 800nm.
Embodiment
Introduce embodiments of the invention below, to understanding of the present invention, but the present invention is limited to embodiment absolutely not with further increase.
Embodiment 1:
Adopt rich Zn (or scarce O
2) ZnO target (separate case application), utilize magnetically controlled DC sputtering, be substrate with the simple glass, base vacuum is evacuated to 2.0 * 10
-4Pa is a working gas with the high-purity argon gas, feeds a spot of O in addition
2(O
2The volume percent that accounts 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, use radio-frequency magnetron sputter method, sputter 60min under identical base vacuum, atmosphere, air pressure and range condition.The film sample thickness that makes under two kinds of conditions is 800nm.
Fig. 1 is the transmitted spectrum of the ZnO film sample for preparing under two kinds of conditions, can see that film reaches more than 90% at the average transmittances of visible region, even to near-infrared region (2200nm), still keeps 90% transmitance nearly.Fig. 2 is the X-ray diffractogram of the ZnO film sample for preparing under two kinds of conditions.Visible by result among the figure, obtained ZnO film is (002) crystal orientation preferential growth, and the obtained film of d.c. sputtering shows stronger crystallinity.The result shows, under identical thickness condition, the present invention utilizes the ZnO film of direct current magnetron sputtering process preparation to have with radio-frequency sputtering to prepare the suitable very high visible and near-infrared band transmitance of film, and shows stronger crystallinity.
Fig. 3, Fig. 4 are the surface topography AFM figure of the ZnO film sample for preparing under two kinds of conditions.Surfaceness (RMS) result by Fig. 4 can find out, under identical thickness condition, the present invention utilizes the high resistant ZnO film (RMS:27.6nm) of direct current magnetron sputtering process preparation to have with radio-frequency sputtering to prepare the suitable surfaceness of film (RMS:25.8nm).
Embodiment 2:
In the application in thin-film solar cells and photoelectric device field, the thickness of high resistant ZnO film generally is controlled between 60～120nm.The sintering temperature sintering that the present embodiment employing is 850 ℃ 20 hours makes rich zinc attitude Zn
1.13The broad stopband stupalith target of O structure utilizes magnetically controlled DC sputtering, is substrate with the simple glass, and base vacuum is evacuated to 2.0 * 10
-4Pa is a working gas with the high-purity argon gas, feeds a spot of O in addition
2(O
2Account for total gas couette 0.5%), operating air pressure maintains 1.2Pa, target and substrate distance are set to 7cm, sputtering power is 80W, depositing time is 4min.The film sample thickness that makes is 80nm.
Fig. 5 can see for the transmitted spectrum of ZnO film sample of preparation, and film nearly reaches 90% at the average transmittances of visible region, even to near-infrared region (2200nm), still keep 90% transmitance.The X-ray diffractogram of the thick sample of 800nm that Fig. 6 prepares down for the same terms among ZnO film sample and the embodiment 1 of preparation.The result shows that the thick ZnO film of obtained 80nm has demonstrated certain crystallinity, is (002) crystal orientation preferential growth.The test result of electrical property shows, makes 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) the ZnO target, utilize magnetically controlled DC sputtering, be substrate with the simple glass, base vacuum is evacuated to 2.0 * 10
-4Pa is a working gas with pure high-purity argon gas, and 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.The film sample thickness that makes is 80nm.The test result of electrical property shows, under the condition of present embodiment, makes sample resistivity about 7 * 10
5Ω cm is lower than embodiment 2 slightly, visible light until the near-infrared region (400～2200nm) average transmittanceies 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) the ZnO target, utilize magnetically controlled DC sputtering, be substrate with the silica glass, base vacuum is evacuated to 2.0 * 10
-4Pa is a working gas with the high-purity argon gas, feeds a spot of O in addition
2(O
2Account for total gas couette 1.0%), operating air pressure maintains 0.8Pa, target and substrate distance are set to 9cm, sputtering power is 50W, depositing time is 12min.The film sample thickness that makes is about 100nm.The test result of electrical property shows, makes sample resistivity about 8 * 10 under this implementation condition
6Ω cm, a little more than embodiment 2, visible light until the near-infrared region (400～2200nm) average transmittanceies 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) the ZnO target, utilize magnetically controlled DC sputtering, be substrate with the simple glass, base vacuum is evacuated to 2.0 * 10
-4Pa is a working gas with the high-purity argon gas, feeds a spot of O in addition
2(O
2Account for total gas couette 0.3%), operating air pressure maintains 0.5Pa, target and substrate distance are set to 10cm, sputtering power is 120W, depositing time is 2min.The film sample thickness that makes is about 60nm.The test result of electrical property shows, makes sample resistivity about 3.4 * 10 under this implementation condition
4Ω cm is lower than embodiment 2, and (400～2200nm) average transmittanceies are higher than 90%, a little more than embodiment 2, meet the application requiring of thin-film solar cells Window layer and diffusion impervious layer and other photoelectric device until the near-infrared region at visible light.
Embodiment 6:
Adopt rich Zn (or scarce O
2) the ZnO target, utilize magnetically controlled DC sputtering, be substrate with organic flexible materials polyimide (PI), base vacuum is evacuated to 2.0 * 10
-4Pa is a working gas with the high-purity argon gas, feeds a spot of O in addition
2(O
2Account for total gas couette 1.5%), operating air pressure maintains 3.0Pa, target and substrate distance are set to 8cm, sputtering power is 100W, depositing time is 5min.The film sample thickness that makes is about 70nm.The test result of electrical property shows, makes sample resistivity about 6 * 10 under this implementation condition
7Ω cm is higher than embodiment 2, and (400～2200nm) average transmittanceies all about 90%, a little less than embodiment 2, meet the application requiring of thin-film solar cells Window layer and diffusion impervious layer and other photoelectric device until the near-infrared region at visible light.
Embodiment 7:
Adopt homemade rich Zn (or scarce O
2) the ZnO target, utilize magnetically controlled DC sputtering, be substrate with the simple glass, base vacuum is evacuated to 2.0 * 10
-4Pa is a working gas with the high-purity argon gas, feeds a spot of O in addition
2(O
2Account for total gas couette 0.3%), operating air pressure maintains 2.0Pa, target and substrate distance are set to 5cm, sputtering power is 40W, depositing time is 8min.The film sample thickness that makes is about 100nm.The test result of electrical property shows, makes sample resistivity about 6 * 10 under this implementation condition
6Ω cm, suitable with embodiment 2, visible light until the near-infrared region (400～2200nm) average transmittanceies 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) the ZnO target, utilize magnetically controlled DC sputtering, be substrate with the simple glass, base vacuum is evacuated to 2.0 * 10
-4Pa is a working gas with the high-purity argon gas, feeds a spot of O in addition
2(O
2Account for total gas couette 0.3%), operating air pressure maintains 2.0Pa, target and substrate distance are set to 7cm, sputtering power is 80W, depositing time is 5min.The film sample thickness that makes is about 100nm.The test result of electrical property shows, makes sample resistivity about 7.5 * 10 under this implementation condition
7Ω cm is higher than embodiment 2, visible light until the near-infrared region (400～2200nm) average transmittanceies 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) the ZnO target, utilize magnetically controlled DC sputtering, be substrate with the simple glass, base vacuum is evacuated to 2.0 * 10
-4Pa is a working gas with the high-purity argon gas, feeds a spot of O in addition
2(O
2Account for total gas couette 0.3%), operating air pressure maintains 0.5Pa, target and substrate distance are set to 9cm, sputtering power is 60W, depositing time is 8min.The film sample thickness that makes is about 120nm.The test result of electrical property shows, makes sample resistivity about 7.2 * 10 under this implementation condition
6Ω cm, a little more than embodiment 2, (400～2200nm) average transmittanceies are about about 90%, a little less than embodiment 2, meet the application requiring of thin-film solar cells Window layer and diffusion impervious layer and other photoelectric device until the near-infrared region at visible light.
Structural formula described in the above embodiment 1-9 is Zn
1+xO or ZnO
1-x, 0.05＜X≤0.2 ceramic target is that the preparation of rich zinc or anoxybiotic zinc oxide may further comprise the steps:
A) prepared burden according to the mole proportioning in zinc source and oxygen source, obtain the nano-ZnO precursor powder of high reactivity, high crystalline then through mix, oven dry and grinding;
B) step a preparation with high performance precursor powder granulation, by waiting the moulded section of static pressure means, the biscuit of ceramics of preparation high compacted density;
C) adopt two crucibles up and down, sink to graphite in the following crucible, in last crucible, insert the ZnO biscuit of ceramics that step b suppresses and be inverted on time crucible; Sintering under 900 ℃ the sintering temperature is less than or equal in employing, makes said rich Zn or scarce O
2Zinc-oxide-base wide-bandgap stupalith target;
Described zinc source is selected from one or more in metallic zinc, zinc oxide, zinc acetate, zinc oxalate, zinc citrate, zinc nitrate, zinc sulfate, zinc fluoride and the zinc chloride;
The said oxygen source that contains is: one or more in ammoniacal liquor, sodium hydroxide, Pottasium Hydroxide, urea, thiocarbamide and the hydrazine.
The sintering temperature that step c adopts is 500-900 ℃.
Sintering time is 2-24 hour under described sintering temperature.
Claims (10)
1. method of utilizing magnetically controlled DC sputtering to prepare the high resistance transparent ZnO film is characterized in that:
(1) utilizing rich zinc or anoxybiotic zno-based target, is substrate with simple glass, silica glass or organic flexible materials, and control base vacuum degree is 1.0 * 10
-4-3.0 * 10
-4Pa;
(2) mixed gas with rare gas element and oxygen is a working gas; Through power, time, the pressure of working gas and the distance between target and substrate of control magnetron sputtering, the ZnO film of preparing n type high resistance transparent is to substitute the technology of traditional rf magnetron sputtering;
The structural formula of described rich zinc or anoxybiotic zno-based target is Zn
1+xO or ZnO
1-x, 0.05＜X in the formula≤0.2;
The volume percent that oxygen accounts for total tolerance in the described working gas is for greater than 0-1.5%;
Distance between described target and substrate is 5-10cm;
The power of described magnetron sputtering is 40-120w.
2. by the described method of claim 1, it is characterized in that described rare gas element is a high-purity argon, the percent by volume of argon gas is >=99.9%.
3. by the described method of claim 1, it is characterized in that the sputtering sedimentation time is 2-15min.
4. by the described method of claim 1, it is characterized in that the distance between target and substrate is 7-8cm.
5. by the described method of claim 1, the pressure that it is characterized in that working gas is 0.5-3Pa.
6. by the described method of claim 1, it is characterized in that described sputtering power is 70-80W.
7. by claim 1,4 or 6 described methods, the resistivity of the n type high resistant zinc-oxide film that it is characterized in that preparing is 10
4-10
8Ω cm.
8. by claim 1,4 or 6 described methods, the thickness of the n type high resistant zinc-oxide film that it is characterized in that preparing is 60-80nm, and in (002) crystal orientation preferential growth.
9. by the described method of claim 1, it is characterized in that:
(1) utilize the high resistant ZnO film of dc sputtering preparation to have the suitable surfaceness of high resistant ZnO film for preparing with radio-frequency sputtering;
(2) the high resistant ZnO film that utilizes dc sputtering preparation visible light near infrared region average transmittances all greater than or near 90%.
10. by the described method of claim 1, it is characterized in that the high resistant zinc-oxide film for preparing meets the requirement of CIGS thin-film solar cells Window layer and diffusion impervious layer.
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