CN102931285A - Method for preparing niobium-doped titanium dioxide transparent conducting film - Google Patents
Method for preparing niobium-doped titanium dioxide transparent conducting film Download PDFInfo
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- CN102931285A CN102931285A CN2012104690933A CN201210469093A CN102931285A CN 102931285 A CN102931285 A CN 102931285A CN 2012104690933 A CN2012104690933 A CN 2012104690933A CN 201210469093 A CN201210469093 A CN 201210469093A CN 102931285 A CN102931285 A CN 102931285A
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Abstract
The invention discloses a method for preparing a niobium-doped titanium dioxide transparent conducting film. The method comprises the following steps: firstly, preparing an oxide ceramic target codoping TiO2 and Nb2O5, and secondly, preparing the niobium-doped titanium dioxide transparent conducting film through a magnetron sputtering method. The niobium-doped titanium dioxide transparent conducting film prepared through the method is greatly increased in concentration of current carriers, and better in electric conductivity, the refractive index is up to 2.4-2.7, higher than that of ITO and AZO, and perfectly matched with that of the thin film silicon material, so that the reduction of the loss of light rays transferred on two dielectric interfaces is facilitated, the transmittance of light rays and the absorptivity of a cell to light are increased, the photoelectric conversion efficiency of a cell is improved, the niobium-doped titanium dioxide transparent conducting film is suitable for a front electrode for a silicon-based thin film solar cell, particularly for a front electrode for an amorphous silicon/microcrystalline silicon laminated cell, and is more stable in the atmosphere of high-reducibility gas compared with ITO, FTO and AZO, and the performance is not affected due to reduction, and accordingly the photoelectric properties that the transparent conducting film is used as the front electrode are maintained.
Description
Technical field
The present invention relates to the photoelectric semiconductor material field, particularly the preparation method of the titania-doped nesa coating of a kind of niobium.
Background technology
The transparent conductive oxide film TCO that uses in the prior art, such as ITO, AZO, FTO etc., they all are subject to the restriction of certain material inherent shortcoming, such as refractive index not high (approximately about 1.8～2), unsteadiness in the plasma atmosphere (high reducing atmosphere such as hydrogen) etc., with it during as the front electrode of silicon-based film solar cells, because itself and silicon thin film refractive index difference bottle strength effect large and that the hull cell photoelectric conversion efficiency that the not high factor of infrared reflectivity causes is promoted has just manifested out, and the key that addresses this problem is to seek comparatively stable film in high reducibility gas hydrogen gas plasma of higher while of a kind of refractive index, and its photoelectric properties and traditional TCO are comparatively approaching, to be adapted to the demand of silicon-based film solar cells.
Summary of the invention
Be subject to the restriction of intrinsic fault in material for conventional nesa coating in the prior art, exist refractive index not high, instable deficiency in the Reductive plasma atmosphere, the present invention proposes a kind of preparation method with titania-doped nesa coating of high stability niobium in high index of refraction, the Reductive plasma atmosphere.
The preparation method of the titania-doped nesa coating of a kind of niobium is characterized in that, comprises following key step:
(1) preparation TiO
2With Nb
2O
5The oxide ceramics target of mixing altogether
With TiO
2, Nb
2O
5The pure powder of analysis be primary raw material, purity is 4N～5N, according to TiO
2With Nb
2O
5Mass ratio be (5～12): 1 the batching, compound is put into high temperature silicon molybdenum stove pre-burning 4～5 hours, calcined temperature is 820～850 ℃; Then the powder finished of sintering adds the polyvinyl alcohol polymerizer after taking out and being cooled to room temperature, so that powder is carried out granulation, then powder is carried out compressing tablet with powder compressing machine, and being pressed into thickness is that 3～5mm, diameter are the target disk of 40～50mm; Then the target disk of making is put into silicon molybdenum stove and carry out sintering, sintering temperature is 1350～1380 ℃, and temperature retention time is 3～4 hours, then is cooled to room temperature, makes TiO
2With Nb
2O
5The oxide ceramics target of mixing altogether;
(2) magnetron sputtering method prepares the titania-doped nesa coating of niobium
Adopt magnetron sputtering technique, with the target of the middle oxide ceramics target for preparing of step (1) as magnetron sputtering, the titania-doped nesa coating of preparation niobium, wherein Sputtering power density is 3.5～5.5W/cm
2, the used substrate of sputter is soda-lime-silica glass, and the sputter underlayer temperature is 550～650 ℃, and sputtering technology pressure is 0.8～1.2Pa, and the distance of target and substrate is 3～5cm, sputter background pressure is 3 * 10
-4～1 * 10
-4Pa also passes into reacting gas except the working gas argon gas in the sputter procedure, sputtering time is 15～20 minutes.After preparation is finished, film is annealed under 450～500 ℃ temperature, so far, finish the preparation of the titania-doped nesa coating of niobium.
Described magnetron sputtering method prepares this film, and by the adjustment of technological parameter, the deposition rate of control film is 0.05～0.1nm/s;
Reacting gas in the described magnetron sputtering process is oxygen, and flow is 5～15sccm;
Described film being annealed under 450～500 ℃ temperature, is to anneal under vacuum environment, i.e. pumping high vacuum in the process of Thin-film anneal, and vacuum degree is 5 * 10
-5～1 * 10
-4Pa;
The titania-doped nesa coating of described niobium is specially adapted to the front electrode of front electrode, especially the amorphous silicon/microcrystalline silicon tandem battery of silicon-based film solar cells.
Titanium dioxide is the semi-conducting material of a kind of broad stopband width, be 3.0～3.2eV, this and conventional transparent conductive oxide such as ITO, AZO, FTO is comparatively approaching, and the visible light transmissivity of titanium dioxide and infrared reflectivity are also higher, the refractive index of titanium dioxide is compared ITO simultaneously, AZO etc. are more near the refractive index of silica-base material, the titanium deoxid film that mixes of niobium for example, its refractive index can reach 2.4～2.7, so that nesa coating and silicon thin film refractive index are more mated, interface loss in the light transmission process is less, thereby is conducive to the absorption with battery of seeing through of light.While is owing to niobium ion mixing, carrier concentration is greatly increased, film conductivity can be better, thereby make it possess the special sheet of nesa coating, become a kind of photoelectric properties better and be particularly suitable for the nesa coating that silicon-based film solar cells, especially amorphous silicon/microcrystalline silicon tandem battery are used.
Advantage of the present invention:
1, with the titania-doped nesa coating of niobium of the present invention during as the front electrode of silicon-based film solar cells, during in particular for the front transparency conductive electrode of amorphous silicon/microcrystalline silicon tandem battery, because the titania-doped nesa coating of niobium compares ITO, FTO, AZO is more stable in the atmosphere of high reducibility gas hydrogen, can do not affected its performance by hydrogen reducing, thereby the photoelectric properties of nesa coating as front electrode have been kept, the performance that guarantees solar cell is unaffected, and its result is better than with ITO or FTO, AZO is the thin-film solar cells device of front electrode;
2, niobium ion mixes, carrier concentration is greatly increased, film conductivity can be better, the refractive index of the titania-doped film of niobium reaches 2.4～2.7, higher than ITO, AZO, more mate with the thin film silicon material refractive index, more be conducive to reduce light in the loss of two medium interfaces transmission, the transmitance of increase light and battery improve the cell photoelectric conversion efficiency to Optical Absorption efficient.
3, compare with other oxidic transparent conducting films, the titanium dioxide source is abundant, price is lower, nontoxic pollution-free, is convenient to the cost control in the large-scale industrialization production.
Description of drawings
Fig. 1 is that the titania-doped nesa coating of niobium for preparing of the present invention is at the spectrogram that sees through of visible light wave range;
Fig. 2 is the XRD figure of the titania-doped nesa coating of niobium for preparing of the present invention.
Embodiment
Below in conjunction with specific embodiment the present invention is set forth in detail.
Embodiment 1
(1) according to TiO
2With Nb
2O
5Mass ratio be 10:1, adopting the electronic analysis level to take by weighing respectively purity is i.e. 99.99% the TiO of 4N
2With Nb
2O
5Powder 30g and 3g, baking temperature was 150 ℃ to the baking of powder drying baking oven with abundant removal moisture in 5 hours before the weighing.Load weighted powder is put into mortar grind, so that powder mixes to evenly.The powder that mixes is put into high temperature silicon molybdenum stove carry out pre-burning, temperature is 830 ℃, and the time is 4.5 hours.Burned powder is cooled to room temperature puts into grinding body, and add polyvinyl alcohol polymerizer 10mL, so that powder is carried out granulation.
(2) powder that above-mentioned granulation is good carries out compressing tablet with powder compressing machine, and the pressure of tablet press machine is 35MPa, and pressure gathers way and is 3MPa/min, and being pressed into thickness is that 4mm, diameter are the circular sheet of 40mm;
(3) the above-mentioned target sheet that suppresses is carried out sintering, sintering temperature is 1360 ℃, and heating rate is 3 ℃/min, and temperature retention time is 3.5 hours, then cools to room temperature with the furnace, finishes TiO
2With Nb
2O
5The preparation of the oxide ceramics target of mixing altogether.
(4) the oxide ceramics target for preparing in the step is target, adopts magnetron sputtering technique to prepare the titanium dioxide nesa coating that niobium mixes, and wherein Sputtering power density is 4W/cm
2, sputter temperature is 580 ℃, and sputtering technology pressure is 1Pa, and substrate is the soda-lime-silica glass sheet, is of a size of 2cm * 2cm, and thick is 3.2mm, and the distance of target and glass substrate is 4cm, and sputter background pressure is 2 * 10
-4Pa also passes into reacting gas oxygen except the working gas argon gas in the sputter procedure, the flow of argon gas and oxygen is respectively 180sccm and 10sccm, and sputtering time is 18 minutes.After preparation is finished, film is annealed under 480 ℃ temperature, and anneal in vacuum environment, vacuum degree is 9 * 10
-5Pa so far, just finishes the preparation of the titania-doped nesa coating of niobium.
The titania-doped film of the niobium of above-mentioned preparation is carried out photoelectric properties tests, visible light transmissivity as shown in Figure 1, its visible light mean transmissivity is 81%, resistivity is 5.3 * 10
-4Ohm. centimetre, square resistance is 16 ohm of every squares, carrier concentration is 8.1 * 10
20Cm
-3, mobility is 18cm
2/ V.s.Film XRD represents anatase structured (101) peak stronger as shown in Figure 2, and preferred orientation is obvious.
Embodiment 2
According to TiO
2With Nb
2O
5Mass ratio be 8:1, adopting the electronic analysis level to take by weighing respectively purity is i.e. 99.99% the TiO of 4N
2With Nb
2O
5Powder respectively is 32g and 4g, the other the same as in Example 1, and the titania-doped film of the niobium that so prepares is done respectively the photoelectric properties test, and its visible light mean transmissivity is 72%, and resistivity is 3.2 * 10
-4Ohm. centimetre, square resistance is 12 ohm of every squares, carrier concentration is 9.6 * 10
20Cm
-3, mobility is 12cm
2/ V.s.The film preferred orientation weakens, and occurs the peak of Rutile Type in the structure.
Embodiment 3
According to TiO
2With Nb
2O
5Mass ratio be 6:1, adopting the electronic analysis level to take by weighing respectively purity is i.e. 99.99% the TiO of 4N
2With Nb
2O
5Powder respectively is 24g and 4g, the other the same as in Example 1, and the titania-doped film of the niobium that so prepares is done respectively the photoelectric properties test, and its visible light mean transmissivity is 69%, and resistivity is 4.1 * 10
-4Ohm. centimetre, square resistance is 23 ohm of every squares, carrier concentration is 7.6 * 10
20Cm
-3, mobility is 8cm
2/ V.s.The film preferred orientation weakens, and occurs the peak of Rutile Type in the structure.
The above only is preferred embodiment of the present invention, is not the present invention is done any pro forma restriction; Any those of ordinary skill in the art, do not breaking away from the technical solution of the present invention scope situation, all can utilize method and the technology contents of above-mentioned announcement that technical solution of the present invention is made many possible changes and modification, or be revised as the equivalent embodiment of equivalent variations.Therefore, every content that does not break away from technical solution of the present invention, any simple modification of above embodiment being done according to technical spirit of the present invention, be equal to replacements, equivalence changes and modify, all still belong in the scope that technical solution of the present invention protects.
Claims (5)
1. the preparation method of the titania-doped nesa coating of niobium is characterized in that, may further comprise the steps:
(1) preparation TiO
2With Nb
2O
5The oxide ceramics target of mixing altogether
With TiO
2, Nb
2O
5The pure powder of analysis be primary raw material, purity is 4N～5N, according to TiO
2With Nb
2O
5Mass ratio be (5～12): 1 the batching, put into high temperature silicon molybdenum stove pre-burning 4～5 hours after the mixing, calcined temperature is 820～850 ℃; The powder that pre-burning is finished adds the polyvinyl alcohol polymerizer after being cooled to room temperature, so that powder is carried out granulation, then carries out compressing tablet with powder compressing machine, and being pressed into thickness is that 3～5mm, diameter are the target disk of 40～50mm; Then the target disk of making is put into silicon molybdenum stove and carry out sintering, sintering temperature is 1350～1380 ℃, and temperature retention time is 3～4 hours, then is cooled to room temperature, makes TiO
2With Nb
2O
5The oxide ceramics target of mixing altogether;
(2) magnetron sputtering method prepares the titania-doped nesa coating of niobium
Adopt magnetron sputtering technique, with the target of the middle oxide ceramics target for preparing of step (1) as magnetron sputtering, the titania-doped nesa coating of preparation niobium, wherein Sputtering power density is 3.5～5.5W/cm
2, the used substrate of sputter is soda-lime-silica glass, and the sputter underlayer temperature is 550～650 ℃, and sputtering technology pressure is 0.8～1.2Pa, and the distance of target and substrate is 3～5cm, sputter background pressure is 3 * 10
-4～1 * 10
-4Pa also passes into reacting gas except the working gas argon gas in the sputter procedure, sputtering time is 15～20 minutes, after preparation is finished, film is annealed under 450～500 ℃ temperature, so far, finishes the preparation of the titania-doped nesa coating of niobium.
2. the preparation method of the titania-doped nesa coating of a kind of niobium according to claim 1 is characterized in that, the deposition rate that the middle magnetron sputtering of step (2) prepares the titania-doped nesa coating of niobium is 0.05～0.1nm/s.
3. the preparation method of the titania-doped nesa coating of a kind of niobium according to claim 1 is characterized in that, the reacting gas that the middle magnetron sputtering of step (2) prepares the titania-doped nesa coating of niobium is oxygen, and flow is 5～15sccm.
4. the preparation method of the titania-doped nesa coating of a kind of niobium according to claim 1 is characterized in that, film is to anneal under vacuum environment in the step (2), and vacuum degree is 5 * 10
-5～1 * 10
-4Pa.
5. the preparation method of the titania-doped nesa coating of a kind of niobium according to claim 1, it is characterized in that, the titania-doped nesa coating of described niobium is applicable to the front electrode of silicon-based film solar cells, especially the front electrode of amorphous silicon/microcrystalline silicon tandem battery.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105951053A (en) * | 2016-05-20 | 2016-09-21 | 郑州大学 | Production method for titanium dioxide transparent conductive oxide mixed with niobium and titanium dioxide transparent conductive oxide mixed with niobium |
| CN106191775A (en) * | 2015-09-18 | 2016-12-07 | 北京大学深圳研究生院 | A kind of transparent conductive film and its preparation method and application |
| CN106298988A (en) * | 2016-10-10 | 2017-01-04 | 江苏神科新能源有限公司 | A kind of heterojunction solar battery and preparation method thereof |
| CN106756791A (en) * | 2016-12-27 | 2017-05-31 | 苏州思创源博电子科技有限公司 | A kind of preparation method of titanium dioxide conductive film |
| CN108689610A (en) * | 2018-06-26 | 2018-10-23 | 浙江大学 | A kind of titania-doped coated glass of niobium and preparation method thereof |
| CN109507764A (en) * | 2018-11-27 | 2019-03-22 | 北京富兴凯永兴光电技术有限公司 | A kind of optical filming material and preparation method, optical anti-reflective film |
| CN114351176A (en) * | 2021-12-01 | 2022-04-15 | 电子科技大学长三角研究院(湖州) | Method and device for preparing hydrogen by water decomposition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102365385A (en) * | 2009-03-27 | 2012-02-29 | 吉坤日矿日石金属株式会社 | Ti-Nb oxide sintered body sputtering target, Ti-Nb oxide thin film, and method for producing the thin film |
-
2012
- 2012-11-20 CN CN2012104690933A patent/CN102931285A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102365385A (en) * | 2009-03-27 | 2012-02-29 | 吉坤日矿日石金属株式会社 | Ti-Nb oxide sintered body sputtering target, Ti-Nb oxide thin film, and method for producing the thin film |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106191775A (en) * | 2015-09-18 | 2016-12-07 | 北京大学深圳研究生院 | A kind of transparent conductive film and its preparation method and application |
| CN105951053A (en) * | 2016-05-20 | 2016-09-21 | 郑州大学 | Production method for titanium dioxide transparent conductive oxide mixed with niobium and titanium dioxide transparent conductive oxide mixed with niobium |
| CN105951053B (en) * | 2016-05-20 | 2018-06-19 | 郑州大学 | A kind of preparation method of titania-doped transparent conductive film of niobium and the titania-doped transparent conductive film of niobium |
| CN106298988A (en) * | 2016-10-10 | 2017-01-04 | 江苏神科新能源有限公司 | A kind of heterojunction solar battery and preparation method thereof |
| CN106756791A (en) * | 2016-12-27 | 2017-05-31 | 苏州思创源博电子科技有限公司 | A kind of preparation method of titanium dioxide conductive film |
| CN108689610A (en) * | 2018-06-26 | 2018-10-23 | 浙江大学 | A kind of titania-doped coated glass of niobium and preparation method thereof |
| CN109507764A (en) * | 2018-11-27 | 2019-03-22 | 北京富兴凯永兴光电技术有限公司 | A kind of optical filming material and preparation method, optical anti-reflective film |
| CN114351176A (en) * | 2021-12-01 | 2022-04-15 | 电子科技大学长三角研究院(湖州) | Method and device for preparing hydrogen by water decomposition |
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Application publication date: 20130213 |