CN101560642B - Method for preparing In2O3 transparent conductive film with high mobility doped with Mo - Google Patents
Method for preparing In2O3 transparent conductive film with high mobility doped with Mo Download PDFInfo
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- CN101560642B CN101560642B CN2009100689687A CN200910068968A CN101560642B CN 101560642 B CN101560642 B CN 101560642B CN 2009100689687 A CN2009100689687 A CN 2009100689687A CN 200910068968 A CN200910068968 A CN 200910068968A CN 101560642 B CN101560642 B CN 101560642B
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Abstract
The invention relates to a method for preparing a Mo-doped In2O3 (namely In2O3: Mo-IMO) transparent conductive film with high-mobility by using the electron beam evaporation technology. The growth of the IMO film by the technology is divided into two stages, wherein a high-purity ceramic target In2O3:MoO3 and O2 are taken as raw materials, and the temperature of a substrate is between 330 and 400 DEG C, the O2 partial pressure is between 5.0-9.0*10<-2>Pa. The method comprise the following steps: growing a layer of buffer layer IMO film at a low velocity of 0.1-0.2 A/s with a film thickness of 30-40nm by using the technology; and secondly, increasing the growth velocity to 0.4 and 1.0 A/s, and growing the IMO film at a high velocity, wherein the thickness of the film is 50-80nm. The typical film resistivity is 2.5*10<-4>ohm cm; the square resistance is 22.5 ohm; the carrier concentration is 5.8*10<20>ohm cm; the electron mobility is 47.1 cm<2>V<-1>s<-1>; and the average transmission of visible light and near infrared regions is 80 percent. The photoelectric properties of the IMO film obtained by the technology are equivalent to or better than that of a film which is grown by utilization of low velocity, and the growth time of the film is greatly reduced.
Description
[technical field]: the invention belongs to the transparent conductive oxide film technical field, particularly be fit to the preparation method of the transparent conductive film of thin film solar cell application.
[background technology]: the optical bandwidth of amorphous silicon hydride (a-Si:H) is about 1.7eV, its uptake factor is higher in the shortwave direction, and the optical bandwidth of microcrystalline hydrogenated silicon (μ c-Si:H) is about 1.1eV, its uptake factor is higher in the long wave direction, and can absorb the near infrared Long wavelength region, absorbing wavelength can extend to 1100nm, and this just makes solar spectrum can obtain more good utilisation.Fig. 1 has provided optical wavelength and the relation between absorption intensity and the uptake factor (Fig. 1 a is the graph of a relation of photon energy and absorption intensity, and Fig. 1 b is the graph of a relation of uptake factor and photon wavelength) of a-Si:H, μ c-Si:H material.In addition, than amorphous silicon thin-film materials, microcrystalline silicon film material structure order degree height, therefore, the microcrystalline silicon film battery has good device stability, does not have obvious decay.This shows that microcrystalline silicon solar cell can utilize the near infrared light zone of solar spectrum preferably, and novel a-Si:H/ μ c-Si:H laminated film solar battery will be expanded the solar spectrum range of application, whole stability test and the efficient of improving
[1-2]
According to the Drude theory, the optical characteristics of near-infrared region is closely related with the carrier concentration of material, and the square root of its plasma frequency and free carrier concentration is proportional
[3]:
Wherein, ω
p-plasma frequency, n
e-electron density, e-elementary electronic charge, m*-effective electron mass.If the higher absorption that has then strengthened near infrared light of carrier concentration.Therefore, based on μ c-Si:H and a-Si:H/ μ c-Si:H laminate film battery applications, wish preceding electrode TCO in the p-i-n type battery structure at visible-range and near infrared region high permeability and keep high conductivity, valid approach is to prepare low carrier concentration and the TCO film of high mobility.Utilize the poor (Mo of high valence state
6+And In
3+The valence state difference be 3) adulterated In
2O
3: Mo (Mo doping In
2O
3, i.e. IMO) and film adapted to application development in this respect.
The method of growth IMO film is a lot of at present, comprises radio frequency/d.c. sputtering (RF/DC Sputtering), electric beam evaporation (EBRE), pulsed laser deposition technique (PLD) etc.Calendar year 2001, the Meng Yang of Fudan University
[4-6]Deng having reported that novel high mobility TCO film-IMO (is Mo doping In
2O
3, In
2O
3: Mo), be characterized in utilizing the poor (Mo of high valence state
6+And In
3+The valence state difference be 3) low-doped enough free carriers that provides mix to be provided, effectively reduce ionized impurity scattering, improve electronic mobility.Typical case IMO electronic mobility 80-130cm
2/ Vs, resistivity~1.8-3 * 10
-4Ω cm, the visible light average transmittances is better than and the near-infrared region (average transmittances of λ=800-1400nm) all~more than 80%, film thickness~250-400nm wherein.E.Elangovan etc.
[7]Utilized radio-frequency sputtering technical study power and film thicknesses etc. are to In
2O
3: the influence of Mo-IMO membrane structure and photoelectric properties, the lowest resistivity of IMO film are 2.65 * 10
-3Ω cm, and high mobility obtains numerical value~19.5cm at decrystallized film
2/ Vs.C.Warmsingh etc.
[8]Utilize the pulsed laser deposition technique In that on glass substrate and monocrystalline 100YSZ (yttria-stabilized zirconia) substrate, grown
2O
3: Mo, i.e. IMO film, experiment shows that the film of 2wt.%Mo doping target preparation has best film characteristics, can obtain the thin film electronic mobility on the YSZ single-crystal substrate and reach~95cm
2/ Vs, through normalized obtain the IMO film in visible-range transmitance greater than 90%.C.C.Kuo etc.
[9]Utilize ion beam assisted deposition to study oxygen partial pressure to In
2O
3: the influence of Mo film microstructure and photoelectric properties, FE-SEM test shows IMO has columnar structure, the AFM test data shows that its r.m.s. roughness is 2nm, oxygen flow increases the resistivity that can reduce the IMO film, the IMO film that obtains when at 5sccm oxygen flow and ion beam voltage 150V has optimum performance, and lowest resistivity is 1.59 * 10
-3Ω cm, electronic mobility~16.31cm
2/ Vs, carrier concentration~1.02 * 10
20/ cm
3Shi-Yao Sun etc.
[10]Utilize the high density plasma evaporation technique to prepare molybdenum doped indium oxide (IMO) film, the target of use is for mixing MoO
3In
2O
3Oxide target wherein contains 2wt.% MoO
3During preparation IMO film at Ar and O
2Add certain amount of H in the mixed gas
2, add H
2The rear film mobility increases, and film resiativity obviously reduces and the process window broadening, but adds H
2Film is reduced in the transmitance of visible region.The Miu Weina of Fudan University (Wei-na miao) etc.
[11]Oxygen partial pressure, substrate temperature and the sputtering current influence to IMO membrane structure and optical property that utilized the magnetically controlled DC sputtering technical study, the lowest resistivity that obtains the IMO film is 3.65 * 10
-4Ω cm, carrier mobility is up to 50cm
2/ Vs, the average transmittance of visible region (containing substrate of glass) is higher than 80%, and wherein the carrier mobility of IMO film mainly is subjected to the influence of crystal boundary scattering.
In film growth techniques, promptly to improve growth velocity, reduce the film growth time, can guarantee that again the material photoelectric properties are important topics of research.The present invention utilizes electron beam evaporation technique, by gradient growth velocity technology, prepares the high mobility of high growth rates and excellent property, and high electricity is led the IMO film with high permeability.
[summary of the invention]: the objective of the invention is to solve the relatively poor relatively problem of film performance under the high speed deposition condition, a kind of electron beam evaporation technique that utilizes is provided, prepare the method for high mobility IMO transparent conductive film by the gradient growth velocity.
The Mo doping In of preparation high mobility provided by the invention, high conductivity and visible light and near infrared region high permeability
2O
3The method of transparent conductive film is to utilize the electric beam evaporation technology, is realized by following steps:
The first, high purity ceramic target In
2O
3: MoO
3(MoO
3Content is the adulterated In of 0.5%-2% weight ratio
2O
3, mix as 0.5% weight ratio) and O
2As source material, base substrate temperature T=330-400 ℃ (as 350 ℃, 380 ℃); O
2Dividing potential drop 5.0-9.0 * 10
-2Pa is as 7.7 * 10
-2Pa;
The second, at first, utilize electron beam evaporation technique low rate on glass substrate
(as
) growth one deck buffer layer Mo doping In
2O
3Film, film thickness 30-40nm (as d=30nm); Secondly, on above-mentioned buffer layer basis, two-forty again
(as
) film of growth 50-80nm (as d=50nm) thickness; Growing film structure: glass/ low rate buffer layer IMO/ two-forty IMO film.
Advantage of the present invention and positively effect:
The present invention utilizes the method for gradient growth velocity, is guaranteeing to utilize low speed buffer layer technology under the higher growth velocity condition, prepare with the low rate condition under identical or better film characteristics, and greatly reduced the film growth time.
The IMO film of growing under (gradient growth velocity) condition, film rectangular resistance is 22.5 Ω, resistivity is 2.5 * 10
-4Ω cm, carrier concentration is 5.8 * 10
20Cm
-3, electronic mobility reaches 47.1cm
2V
-1s
-1, visible light and near infrared range average transmittances~80% (containing 2mm thickness glass substrate).
[description of drawings]:
Fig. 1 has provided optical wavelength and the relation between absorption intensity and the uptake factor (Fig. 1 a is the graph of a relation of photon energy and absorption intensity, and Fig. 1 b is the graph of a relation of uptake factor and photon wavelength) of a-Si:H, μ c-Si:H material.
Fig. 2 is that growth velocity is respectively
With
The IMO film surface appearance figure that grows under (gradient growth velocity) condition.(Fig. 2 a is that growth velocity is
The IMO film surface appearance figure that grows under the condition; Fig. 2 b is that growth velocity is
The IMO film surface appearance figure that grows under the condition; Fig. 2 c is that growth velocity is
The IMO film surface appearance figure that grows under (gradient growth velocity) condition.)
[embodiment]:
Embodiment 1:
The concrete manufacturing processed of the growth IMO film process that the present invention proposes is as follows:
1, electron beam evaporation technique is initially at low rate
Growth IMO film 30nm under the condition is as buffer layer;
2, secondly, under the constant situation of other growth conditionss, two-forty on above-mentioned buffering basis
Growth 50nmIMO film, the film that final growth obtains is the IMO film of 80nm thickness, membrane structure:
Above-mentioned thickness is the thickness of quartz resonator test in the film growth system, and the film thickness of actual measurement is 110nm.
Typical growth conditions is as follows: electron beam evaporation technique growth IMO film, and the glass substrate area is 10cm * 10cm, growth temperature is set at 350 ℃, background vacuum pressure 3.0 * 10
-3Pa feeds high-purity O
2Operating air pressure 7.7 * 10 during gas
-2Pa utilizes high purity In
2O
3: MoO
3Target (MoO
3: 0.5% weight ratio), electron beam gun operating voltage 6380V, electronic beam current 14-22mA (low rate
Employing~14mA and two-forty
Adopt~22mA).
Film performance is seen accompanying drawing 2, accompanying drawing 3 and table 1.As can be seen, membrane structure is
Sample in, the film grain-size is bigger, and film is in the transmitance of visible-range and low rate growth
The transmitance of film is suitable, and grows than two-forty
The transmitance height of film.In addition, under the situation of equal film thickness, the growth of gradient speed
The square resistance of film is minimum, and electronic mobility is the highest, and film has good electric property.
Table 1 growth velocity is respectively
With
The electric property of the IMO film of growing under (gradient growth velocity) condition
Embodiment 2
The concrete manufacturing processed of film:
1, electron beam evaporation technique is initially at low rate
Growth IMO film 40nm under the condition is as buffer layer;
2, secondly, under the constant situation of other growth conditionss, two-forty on above-mentioned buffering basis
Growth 60nmIMO film, the IMO film of the 70nm thickness of finally growing, membrane structure:
Above-mentioned thickness is the thickness of quartz resonator test in the film growth system, actual (real) thickness 120nm.
Typical growth conditions is as follows: electron beam evaporation technique growth IMO film, and the glass substrate area is 10cm * 10cm, growth temperature is set at 350 ℃, background vacuum pressure 3.0 * 10
-3Pa feeds high-purity O
2Operating air pressure 7.7 * 10 during gas
-2Pa utilizes high purity In
2O
3: MoO
3Target (MoO
3: 0.5% weight ratio), electron beam gun operating voltage 6380V, electronic beam current 14-22mA (low rate
Employing~14mA and two-forty
Adopt~22mA).
Reference
[1]J.Meier,S.Dubail,R.Platz,etc.Solar?Energy?Materials?and?Solar?Cells,49(1997)35.
[2]Arvind?Shah,J.Meier,E.Vallat-Sauvain,etc.Thin?Solid?Films,403-404(2002)179.
[3]V.Sittinger,F.Ruske,W.Werner,etc.Thin?Solid?Films?496(2006)16.
[4]Y.Meng,X.L.Yang,H.X.Chen,etc.Thin?Solid?films,394(2001)219.
[5]Y.Meng,X.L.Yang,H.X.Chen,etc.J.Vac.Sci.Tech.A,20(2002)288.
[6] Meng Yang, Yang Xiliang, Chen Huaxian etc., photoelectron technology, 21 (2001) 17.
[7]E.Elangovan,A.Marques,A.S.Viana,etc.Thin?Solid?Films,516(2008)1359.
[8]C.Warmsingh,Y.Yoshida,and?D.W.Readey,etc.Journal?of?Applied?Physics,95(2004)3831.
[9]C.C.Kuo,C.C.Liu,C.C.Lin,etc.Vacuum,82(2008)441.
[10]Shi-Yao?Sun,Jow-Lay?Huang,Ding-Fwu?Lii.Thin?Solid?Films,469-470(2004)6.
[11] Li Xifeng, Miu Weina, Zhang Qun etc., vacuum science and technology journal, 25 (2005) 142.
Claims (1)
1. Mo doping In who prepares high mobility, high conductivity and visible light and near infrared region high permeability
2O
3The method of (being IMO) transparent conductive film is characterized in that this method utilizes the electric beam evaporation technology, is realized by following steps:
The first, high purity ceramic target In
2O
3: MoO
3And O
2As source material, base substrate temperature T=330-400 ℃; O
2Dividing potential drop 5.0-9.0 * 10
-2Pa; Described high purity ceramic target In
2O
3: MoO
3Be MoO
3Content is the adulterated In of 0.5%-2% weight ratio
2O
3
The second, at first, utilize electron beam evaporation technique low rate on glass substrate
Growth one deck buffer layer Mo doping In
2O
3Film, film thickness 30-40nm; Secondly, on above-mentioned buffer layer basis, two-forty again
The film of growth 50-80nm thickness; Growing film structure: glass/low rate buffer layer Mo doping In
2O
3Film/two-forty Mo doping In
2O
3Film.
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CN101792901B (en) * | 2010-04-08 | 2011-06-01 | 山东大学 | Method for preparing cubic indium oxide single-crystal film on yttrium-doped zirconia substrate |
CN103187472A (en) * | 2011-12-30 | 2013-07-03 | 亚树科技股份有限公司 | Thin film solar cell with high infrared light absorptivity and processing method thereof |
CN104846335B (en) * | 2015-05-28 | 2017-06-23 | 深圳大学 | A kind of N-shaped cuprous oxide film and preparation method thereof |
CN114057470A (en) * | 2020-07-31 | 2022-02-18 | 广州市尤特新材料有限公司 | Preparation method of molybdenum-doped indium oxide target material and molybdenum-doped indium oxide target material |
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CN1267061A (en) * | 2000-04-11 | 2000-09-20 | 复旦大学 | Electrically conducting transparent film and its preparing process |
CN101079382A (en) * | 2007-05-24 | 2007-11-28 | 复旦大学 | Near-infrared high-transmission rate and multi-crystal transparent conductive oxide film and its making method |
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CN1267061A (en) * | 2000-04-11 | 2000-09-20 | 复旦大学 | Electrically conducting transparent film and its preparing process |
CN101079382A (en) * | 2007-05-24 | 2007-11-28 | 复旦大学 | Near-infrared high-transmission rate and multi-crystal transparent conductive oxide film and its making method |
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