CN103572202A - Transparent conducting film and preparation method thereof - Google Patents
Transparent conducting film and preparation method thereof Download PDFInfo
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- CN103572202A CN103572202A CN201210267041.8A CN201210267041A CN103572202A CN 103572202 A CN103572202 A CN 103572202A CN 201210267041 A CN201210267041 A CN 201210267041A CN 103572202 A CN103572202 A CN 103572202A
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Abstract
The invention belongs to the field of semiconductor photoelectric materials, and discloses a transparent conducting film and a preparation method thereof. The conducting film comprises a Al2O3 layer for buffering and matching, a CuSn layer for conduction, and a ReO3 layer for a high work function, and the Al2O3 layer, the CuSn layer, and the ReO3 layer form a Al2O3-CuSn-ReO3 sandwich structure. The transparent conducting film provided by the invention is a three-layer anode film of the Al2O3-CuSn-ReO3 sandwich structure; the first Al2O3 layer plays a role of a matching layer; the intermediate CuSn layer mainly plays a role of conduction; the outer ReO3 layer has a high surface work function, and can match energy levels of other functional layers of the device; the film has a sheet resistance of as low as 10 ohms per square, has a visible light transmittance of 92%, and has a surface work function of 6.1 eV.
Description
Technical field
The present invention relates to photoelectric semiconductor material field, relate in particular to a kind of transparent conductive film and preparation method thereof.
Background technology
Transparent conductive film is optical clear performance and conductivity to be compounded in to the photoelectric material of one, because it has excellent photoelectric characteristic, becomes study hotspot and advanced subject in recent years, can be widely used in solar cell, LED, TFT, the screen display fields such as LCD and touch-screen.The raising requiring along with device performance, also improves requiring for the performance of the nesa coating as device anode.Except keeping high visible transmitance, low resistivity, also requiring has higher surface work function, and the energy level of its and other functional layer is matched, and reduces potential barrier, and raising Carrier Injection Efficiency, finally reaches high electrical efficiency.
Current business-like various transparent conductive films, as ITO, AZO, ATO and super thin metal film etc., its light transmission rate, electroconductibility and surface work function are all lower.
Summary of the invention
Based on the problems referred to above, the invention provides a kind of transparent conductive film, this film plays conductive anode effect.
Technical scheme of the present invention is as follows:
, this conductive film comprises the Al as buffering and matching effect
2o
3layer, as the CuSn layer of electric action, and as the ReO of high work content effect
3layer; And Al
2o
3layer, CuSn layer and ReO
3layer forms Al
2o
3-CuSn-ReO
3sandwich structure; Al
2o
3layer, CuSn layer and ReO
3the thickness of layer is respectively 50 ~ 150nm, 5 ~ 55nm and 0.5 ~ 5nm; Preferably, Al
2o
3layer, CuSn layer and ReO
3the thickness of layer is respectively 80nm, 25nm and 2nm.
The preparation method of above-mentioned transparent conductive film provided by the invention, comprises the steps:
S1, substrate, Al target and CuSn alloys target are put into the vacuum chamber of sputtering equipment, and vacuum chamber is vacuumized; Regulate Al target and CuSn alloys target to be set as 35 ~ 90mm with the distance of substrate respectively;
S2, Al
2o
3the preparation of film: use Al target, in passing into the argon gas working gas of vacuum chamber, pass into oxygen, and the operating pressure 0.2 ~ 2.0Pa of argon gas and oxygen mixture in vacuum chamber, oxygen quality percentage composition accounts for 1 ~ 10%, regulate the sputtering power 60 ~ 160W of sputtering equipment, carry out subsequently coating film treatment 2 ~ 5 hours, obtain the Al that thickness is 50 ~ 150nm
2o
3film;
The preparation of S3, CuSn film: use CuSn alloys target, in vacuum chamber, pass into pure argon as working gas, the argon gas operating pressure 0.2 ~ 2.0Pa in vacuum chamber, the sputtering power 30 ~ 100W of adjusting sputtering equipment, carries out coating film treatment 2 ~ 5 hours, subsequently at Al
2o
3on film, obtaining thickness is the Al of the CuSn film of 5 ~ 55nm
2o
3the two-layer sample of-CuSn;
S4, the Al that step S3 is obtained
2o
3the two-layer sample of-CuSn and ReO
3put into the vacuum chamber of evaporated device, the vacuum tightness that vacuum chamber is set is 1.0 * 10
-3pa ~ 1.0 * 10
-6pa; Subsequently at Al
2o
3the ReO that the CuSn thin film layer surface evaporation thickness of the two-layer sample of-CuSn is 0.5 ~ 5nm
3film, obtains Al
2o
3-CuSn-ReO
3the transparent conductive film of sandwich structure.
The preparation method of described transparent conductive film, in step S1, vacuum chamber is vacuumized and adopts mechanical pump and molecular pump to carry out, and the vacuum tightness of vacuum chamber is evacuated to 1.0 * 10
-3pa ~ 1.0 * 10
-6pa; Preferably, the vacuum tightness of vacuum chamber is evacuated to 6.0 * 10
-4pa.
The preparation method of described transparent conductive film, in step S1, Al target and CuSn alloys target are set as 50mm with the distance of substrate respectively.
The preparation method of described transparent conductive film, in step S2, the operating pressure 1.0Pa of argon gas and oxygen mixture in vacuum chamber; Oxygen quality percentage composition accounts for 5%; The sputtering power 100W of sputtering equipment.
The preparation method of described transparent conductive film, in step S3, the operating pressure 1.0Pa of argon gas and oxygen mixture in vacuum chamber; The sputtering power 60W of sputtering equipment.
The preparation method of described transparent conductive film, in step S4, the vacuum tightness of vacuum chamber is 2.0 * 10
-4pa.
The preparation method of described transparent conductive film, described substrate is polyethylene terephthalate (PET), polyethersulfone (PES) or poly-carbon ester (PC).
Transparent conductive film provided by the invention is Al
2o
3-CuSn-ReO
3three layers of anode film of sandwich structure, the first layer Al
2o
3layer plays matching layer, and middle CuSn layer plays main electric action, outer ReO
3there is higher surface work function, can mate with the energy level of other functional layers of device; And the square resistance of this film is low to moderate 15 Ω/mouths, and visible light transmissivity reaches 88%, surface work function 6.1eV, can be used as the anode of the devices such as organic electroluminescent device OLED, organic solar batteries.
What the present invention used is that pressure decatizing electroplating method is prepared three level stack formula Al
2o
3-CuSn-ReO
3transparent conductive film, method is simple, and technique is easily controlled, and can combine with follow-up organic materials evaporation process, and efficiency is higher.
Accompanying drawing explanation
Fig. 1 is the light transmission rate test curve figure that embodiment 1 makes transparent conductive film; Use ultraviolet-visible pectrophotometer to test, test wavelength 300 ~ 900nm.
Embodiment
Below in conjunction with accompanying drawing, preferred embodiment of the present invention is described in further detail.
Al target and CuSn alloys target are packed into sputtering equipment, then, successively use dehydrated alcohol and deionized water ultrasonic cleaning PET substrate, and dry up with high pure nitrogen, put into vacuum cavity.The distance of target and substrate is set as to 50mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into 6.0 * 10
-4pa, prepares the first layer Al
2o
3, passing into the argon gas that contains oxygen, pressure is adjusted to 1.0Pa, and oxygen content accounts for 5%, regulates sputtering power 100W.Then prepare second layer CuSn film, use CuSn alloys target, using pure argon as working gas, pressure selects 1.0Pa, and sputtering power selects 60W, afterwards sample is put into evaporated device, with mechanical pump and molecular pump, the vacuum tightness of cavity is evacuated to 2.0 * 10
-4pa, evaporation ReO
3film.Al
2o
3, CuSn film, ReO
3the thickness that film is three layers is respectively 80nm, 25nm, and 2nm, square resistance is 15 Ω/mouths, visible ray average transmittances is 88%, surface work function 6.1eV.
Fig. 1 is the light transmission rate test curve figure that embodiment 1 makes transparent conductive film; Use ultraviolet-visible pectrophotometer to test, test wavelength 300 ~ 900nm.
As shown in Figure 1, at visible ray 470 ~ 790nm wavelength region average transmittances, reach 83%.
Embodiment 2
Al target and CuSn alloys target are packed into sputtering equipment, successively use dehydrated alcohol and deionized water ultrasonic cleaning PES substrate, and dry up with high pure nitrogen, put into vacuum cavity.The distance of target and substrate is set as to 30mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into 1.0 * 10
-5pa, prepares the first layer Al
2o
3, passing into the argon gas that contains oxygen, pressure is adjusted to 2.0Pa, and oxygen content accounts for 10%, regulates sputtering power 160W.Then prepare second layer CuSn film, use CuSn alloys target, using pure argon as working gas, pressure selects 0.2Pa, and sputtering power selects 30W, afterwards sample is put into evaporated device, with mechanical pump and molecular pump, the vacuum tightness of cavity is evacuated to 1.0 * 10
-6pa, evaporation ReO
3film.Al
2o
3, CuSn film, ReO
3the thickness that film is three layers is respectively 50nm, 35nm, and 0.5nm, square resistance is 9 Ω/mouths, visible ray average transmittances is 83%, surface work function 5.7eV.
Embodiment 3
Al target and CuSn alloys target are packed into sputtering equipment, successively use dehydrated alcohol and deionized water ultrasonic cleaning PC substrate, and dry up with high pure nitrogen, put into vacuum cavity.The distance of target and substrate is set as to 90mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into 1.0 * 10
-3pa, prepares the first layer Al
2o
3, passing into the argon gas that contains oxygen, pressure is adjusted to 0.2Pa, and oxygen content accounts for 1%, regulates sputtering power 60W.Then prepare second layer CuSn film, use CuSn alloys target, using pure argon as working gas, pressure selects 2.0Pa, and sputtering power selects 60W, afterwards sample is put into evaporated device, with mechanical pump and molecular pump, the vacuum tightness of cavity is evacuated to 1.0 * 10
-3pa, evaporation ReO
3film.Al
2o
3, CuSn film, ReO
3the thickness that film is three layers is respectively 150nm, 5nm, and 5nm, square resistance is 44 Ω/mouths, visible ray average transmittances is 87%, surface work function 5.9eV.
Table 1 is that commercial ito thin film (comparative example 1 ~ 3) makes conductive film the performance test results with embodiment 1 ~ 3; As can be seen from Table 1, under identical resistance and light transmission rate, the Al that embodiment 1 ~ 3 makes
2o
3-CuSn-ReO
3the surface work function of film, all higher than commercial ito thin film, has very large performance advantage.
Table 1
| Thin film layer and thickness thereof | Square resistance | Light transmission rate | Surface | |
| Embodiment | ||||
| 1 | Al 2O 3(80nm)-CuSn(25nm)-ReO 3(2nm) | 15 Ω/mouths | 88% | 6.1eV |
| Embodiment 2 | Al 2O 3(30nm)-CuSn(50nm)-ReO 3(0.5nm) | 9 Ω/mouths | 83% | 5.7eV |
| Embodiment 3 | Al 2O 3(100nm)-CuSn(5nm)-ReO 3(5nm) | 44 Ω/mouths | 87% | 5.9eV |
| Comparative example 1 | ITO(50nm) | 44 Ω/mouths | 87% | 4.6eV |
| Comparative example 2 | ITO(150nm) | 15 Ω/mouths | 88% | 4.7eV |
| Comparative example 3 | ITO(220nm) | 9 Ω/mouths | 83% | 4.8eV |
Should be understood that, the above-mentioned statement for preferred embodiment of the present invention is comparatively detailed, can not therefore think the restriction to scope of patent protection of the present invention, and scope of patent protection of the present invention should be as the criterion with claims.
Claims (10)
1. a transparent conductive film, is characterized in that, this conductive film comprises the Al as buffering and matching effect
2o
3layer, as the CuSn layer of electric action, and as the ReO of high work content effect
3layer; And Al
2o
3layer, CuSn layer and ReO
3layer forms Al
2o
3-CuSn-ReO
3sandwich structure; Al
2o
3layer, CuSn layer and ReO
3the thickness of layer is respectively 50 ~ 150nm, 5 ~ 55nm and 0.5 ~ 5nm.
2. transparent conductive film according to claim 1, is characterized in that, described Al
2o
3layer, CuSn layer and ReO
3the thickness of layer is respectively 80nm, 25nm and 2nm.
3. a preparation method for transparent conductive film, is characterized in that, comprises the steps:
S1, substrate, Al target and CuSn alloys target are put into the vacuum chamber of sputtering equipment, and vacuum chamber is vacuumized; Regulate Al target and CuSn alloys target to be set as 35 ~ 90mm with the distance of substrate respectively;
S2, Al
2o
3the preparation of film: use Al target, in passing into the argon gas working gas of vacuum chamber, pass into oxygen, and the operating pressure 0.2 ~ 2.0Pa of argon gas and oxygen mixture in vacuum chamber, oxygen quality percentage composition accounts for 1 ~ 10%, regulate the sputtering power 60～160W of sputtering equipment, carry out subsequently coating film treatment 2 ~ 5 hours, obtain the Al that thickness is 50 ~ 150nm
2o
3film;
The preparation of S3, CuSn film: use CuSn alloys target, in vacuum chamber, pass into pure argon as working gas, the argon gas operating pressure 0.2 ~ 2.0Pa in vacuum chamber, the sputtering power 30 ~ 100W of adjusting sputtering equipment, carries out coating film treatment 2 ~ 5 hours, subsequently at Al
2o
3on film, obtaining thickness is the Al of the CuSn film of 5 ~ 55nm
2o
3the two-layer sample of-CuSn;
S4, the Al that step S3 is obtained
2o
3the two-layer sample of-CuSn and ReO
3put into the vacuum chamber of evaporated device, the vacuum tightness that vacuum chamber is set is 1.0 * 10
-3pa ~ 1.0 * 10
-6pa; Subsequently at Al
2o
3the ReO that the CuSn thin film layer surface evaporation thickness of the two-layer sample of-CuSn is 0.5 ~ 5nm
3film, obtains Al
2o
3-CuSn-ReO
3the transparent conductive film of sandwich structure.
4. the preparation method of transparent conductive film according to claim 3, is characterized in that, in step S1, vacuum chamber is vacuumized and adopts mechanical pump and molecular pump to carry out, and the vacuum tightness of vacuum chamber is evacuated to 1.0 * 10
-3pa ~ 1.0 * 10
-6pa.
5. the preparation method of transparent conductive film according to claim 4, is characterized in that, in step S1, the vacuum tightness of vacuum chamber is evacuated to 6.0 * 10
-4pa.
6. the preparation method of transparent conductive film according to claim 3, is characterized in that, in step S1, Al target and CuSn alloys target are set as 50mm with the distance of substrate respectively.
7. the preparation method of transparent conductive film according to claim 3, is characterized in that, in step S2, and the operating pressure 1.0Pa of argon gas and oxygen mixture in vacuum chamber; Oxygen quality percentage composition accounts for 5%; The sputtering power 100W of sputtering equipment.
8. the preparation method of transparent conductive film according to claim 3, is characterized in that, in step S3, and the operating pressure 1.0Pa of argon gas and oxygen mixture in vacuum chamber; The sputtering power 60W of sputtering equipment.
9. the preparation method of transparent conductive film according to claim 3, is characterized in that, in step S4, the vacuum tightness of vacuum chamber is 2.0 * 10
-4pa.
10. according to the preparation method of the arbitrary described transparent conductive film of claim 3 to 9, it is characterized in that, in step S1, described substrate is polyethylene terephthalate, polyethersulfone or poly-carbon ester.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210267041.8A CN103572202A (en) | 2012-07-30 | 2012-07-30 | Transparent conducting film and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210267041.8A CN103572202A (en) | 2012-07-30 | 2012-07-30 | Transparent conducting film and preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN103572202A true CN103572202A (en) | 2014-02-12 |
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ID=50044902
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| CN201210267041.8A Pending CN103572202A (en) | 2012-07-30 | 2012-07-30 | Transparent conducting film and preparation method thereof |
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| Country | Link |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI577815B (en) * | 2014-05-21 | 2017-04-11 | 賀利氏德國有限責任兩合公司 | Cusn, cuzn and cu2znsn sputter targets |
| CN106843607A (en) * | 2016-11-15 | 2017-06-13 | 惠州市宝明精工有限公司 | A kind of capacitance touch screen of OnCell of high transmittance and preparation method thereof |
-
2012
- 2012-07-30 CN CN201210267041.8A patent/CN103572202A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI577815B (en) * | 2014-05-21 | 2017-04-11 | 賀利氏德國有限責任兩合公司 | Cusn, cuzn and cu2znsn sputter targets |
| CN106843607A (en) * | 2016-11-15 | 2017-06-13 | 惠州市宝明精工有限公司 | A kind of capacitance touch screen of OnCell of high transmittance and preparation method thereof |
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Application publication date: 20140212 |