CN103311365B - A kind of preparation method of rear-earth-doped C 12 A 7 thin-film material - Google Patents

Abstract

A preparation method of rare earth doped calcium dodecaaluminate thin film material, the invention relates to a preparation method of thin film material. The invention aims to solve the problem that the high price and limited supply of indium limit its application. Methods: 1. mixing; 2. pressing into a raw material sheet; 3. preparing rare earth-doped calcium dodecaaluminate polycrystalline material; 4. sputtering. The transparent conductive property of the thin film prepared by the invention is used to replace the expensive indium tin oxide transparent conductive thin film material, so as to improve the photoelectric conversion efficiency of the solar cell and simultaneously achieve the purpose of simplifying the cell structure and reducing the cost. The invention is used for preparing rare earth-doped calcium dodecaaluminate film material.

Description

A preparation method of rare earth-doped calcium dodecaaluminate film material

technical field

The invention relates to a method for preparing thin film materials.

Background technique

Solar cells use the interaction of sunlight and light-absorbing materials to directly convert light energy into electrical energy. Silicon-based solar cells have always been the focus of research and development. Transparent conductor is an important functional material widely used in solar cells, and the most widely used one is indium tin oxide (ITO) thin film material. However, the high price and limited supply of indium, as well as the fragility and lack of flexibility of the ITO layer limit its application.

Contents of the invention

The invention aims to solve the problem that the application of indium is limited due to the high price and limited supply, and provides a preparation method of rare earth-doped calcium dodecaaluminate thin film material.

A preparation method of a rare earth-doped calcium dodecaaluminate film material, specifically prepared according to the following steps:

1. Mix CaO powder and Al ₂ O ₃ powder evenly, then add rare earth oxide, and then grind for 4h to 6h to obtain mixed powder, in which the ratio of CaO and Al ₂ O ₃ is 12:7, rare earth oxide The ratio of the amount of substance to CaO is 0.042% to 0.42%;

2. Press the mixed powder obtained in step 1 into a raw material sheet under the pressure of 10MPa-20MPa, hold the pressure for 4min-10min;

3. Sintering the raw material sheet obtained in step 2 in an air atmosphere, controlling the sintering temperature to 1200°C to 1400°C, and the sintering time to 10h to 12h, to obtain a polycrystalline material of dodecacalcium heptaaluminate doped with rare earth;

4. Sputter the rare earth-doped calcium dodecaaluminate polycrystalline material obtained in step 3 onto the surface of the substrate by magnetron sputtering. The sputtering parameters are: vacuumize to 6.0×10 ^-4 Pa～9.0× 10 ^-4 Pa, the control sputtering pressure is 1Pa～10Pa, the substrate temperature is 300℃～450℃, the RF power source sputtering power is 90W～120W, the sputtering time is 60min-300min, the argon gas flow rate is 30sccm～50sccm, Then, the film material obtained on the surface of the substrate is subjected to post-reduction treatment to prepare the rare earth doped heptaaluminate calcium dodecaaluminate film material.

The beneficial effects of the present invention are: the present invention prepares rare earth doped calcium heptaaluminate (12CaO·7Al ₂ O ₃ , C12A7) film material, and the raw materials required for the synthesis of C12A7 are high in nature, low in cost, and environmentally friendly it is good. C12A7 does not produce strong light absorption in the visible light field, so it can maintain transparency, and after proper reduction treatment, it can be transformed from an insulator to a conductor through a semiconductor. Through the doping of rare earth ions, such as erbium, ytterbium, thulium, etc., the rare earth doped dodecaaluminate thin film material is prepared, so that it has up (down) conversion luminescence performance and improves the photoelectric conversion efficiency of solar cells.

The invention uses the transparent conductive properties of the prepared RE:C12A7 transparent film to replace the expensive indium tin oxide transparent conductive film material, and at the same time utilizes the up (down) conversion luminescent properties of doped rare earth ions to expand the response limit of solar cells to sunlight To the full spectrum range, improve the photoelectric conversion efficiency of solar cells. Therefore, the design of RE:C12A7 transparent conductive film can achieve the purpose of simplifying the structure of the solar cell and reducing the cost while improving the photoelectric conversion efficiency of the solar cell.

The invention is used for preparing rare earth-doped calcium dodecaaluminate film material.

detailed description

The technical solution of the present invention is not limited to the specific embodiments listed below, but also includes any combination of the specific embodiments.

Specific Embodiment 1: In this embodiment, a method for preparing a rare earth-doped calcium dodecaaluminate thin film material is specifically prepared according to the following steps:

1. Mix CaO powder and Al ₂ O ₃ powder evenly, then add rare earth oxide, and then grind for 4h to 6h to obtain mixed powder, in which the ratio of CaO and Al ₂ O ₃ is 12:7, rare earth oxide The ratio of the amount of substance to CaO is 0.042% to 0.42%;

2. Press the mixed powder obtained in step 1 into a raw material sheet under the pressure of 10MPa-20MPa, hold the pressure for 4min-10min;

3. Sintering the raw material sheet obtained in step 2 in an air atmosphere, controlling the sintering temperature to 1200°C to 1400°C, and the sintering time to 10h to 12h, to obtain a polycrystalline material of dodecacalcium heptaaluminate doped with rare earth;

4. Sputter the rare earth-doped calcium dodecaaluminate polycrystalline material obtained in step 3 onto the surface of the substrate by magnetron sputtering. The sputtering parameters are: vacuumize to 6.0×10 ^-4 Pa～9.0× 10 ^-4 Pa, the control sputtering pressure is 1Pa～10Pa, the substrate temperature is 300℃～450℃, the RF power source sputtering power is 90W～120W, the sputtering time is 60min-300min, the argon gas flow rate is 30sccm～50sccm, Then, the film material obtained on the surface of the substrate is subjected to post-reduction treatment to prepare the rare earth doped heptaaluminate calcium dodecaaluminate film material.

This embodiment uses the transparent conductive properties of the prepared RE:C12A7 transparent film to replace the expensive indium tin oxide transparent conductive film material, and at the same time uses the up (down) conversion luminescence properties of doped rare earth ions to limit the response of solar cells to sunlight. Extend to the full spectrum range and improve the photoelectric conversion efficiency of solar cells. Therefore, the design of RE:C12A7 transparent conductive film can achieve the purpose of simplifying the structure of the solar cell and reducing the cost while improving the photoelectric conversion efficiency of the solar cell.

Embodiment 2: This embodiment differs from Embodiment 1 in that: in step 1, the rare earth oxide is one or more combinations of erbium oxide, ytterbium oxide and thulium oxide. Others are the same as in the first embodiment.

Embodiment 3: The difference between this embodiment and Embodiment 1 is that in step 1, grind for 5 hours. Others are the same as in the first embodiment.

Embodiment 4: This embodiment is different from Embodiment 1 in that: In step 2, under the condition of pressure of 12MPa-18MPa, the pressure is maintained for 5min-8min. Others are the same as in the first embodiment.

Embodiment 5: This embodiment is different from Embodiment 1 to Embodiment 4 in that: in step 2, the pressure is maintained for 7 minutes under the condition of 15 MPa. Others are the same as one of the specific embodiments 1 to 4.

Embodiment 6: This embodiment is different from Embodiment 1 in that: in step 3, the sintering temperature is controlled to be 1250° C. to 1350° C., and the sintering time is 11 hours. Others are the same as in the first embodiment.

Embodiment 7: This embodiment is different from Embodiment 1 to Embodiment 6 in that: in step 3, the sintering temperature is controlled to be 1300°C. Others are the same as one of the specific embodiments 1 to 6.

Embodiment 8: This embodiment is different from Embodiment 1 in that the substrate in step 4 is glass or silicon wafer. Others are the same as in the first embodiment.

Embodiment 9: This embodiment is different from Embodiment 1 to Embodiment 8 in that: the glass is quartz glass. Others are the same as one of the specific embodiments 1 to 8.

Adopt the following examples to verify the beneficial effects of the present invention:

Embodiment one:

In this embodiment, a method for preparing a rare earth-doped calcium dodecaaluminate thin film material is specifically prepared according to the following steps:

1. Mix CaO powder and Al ₂ O ₃ powder evenly, then add rare earth oxide, and then grind for 5 hours to obtain mixed powder, in which the mass of CaO is 2.8g and the mass of Al ₂ O ₃ is 2.9697g, and the mass of rare earth oxide is The mass of Er ₂ O ₃ is 0.0080g, and the mass of Yb ₂ O ₃ is 0.0820g;

2. The mixed powder obtained in step 1 is pressed into a raw material sheet under a pressure of 15 MPa for 5 minutes;

3. Sintering the raw material sheet obtained in step 2 in an air atmosphere, controlling the sintering temperature to 1300° C., and the sintering time to 11 hours to obtain a rare earth-doped calcium dodecaaluminate polycrystalline material;

4. Sputter the rare earth-doped calcium dodecaaluminate polycrystalline material obtained in step 3 onto the surface of the substrate by magnetron sputtering. The sputtering parameters are: vacuum to 9.0×10 ^-4 Pa, controlled sputtering The injection pressure is 5Pa, the substrate temperature is 300°C, the RF sputtering power is 100W, the sputtering time is 120min, and the argon gas flow rate is 40sccm. Calcium dodecaaluminate film material.

The substrate in step 4 of this embodiment is quartz glass; the rare earth doped calcium dodecaaluminate polycrystalline material described in this embodiment is erbium, ytterbium double doped calcium dodecaaluminate polycrystalline material, wherein the erbium ion The molar doping concentration is 1%, and the molar doping concentration of ytterbium ions is 10%.

This example uses the transparent conductive properties of the prepared RE:C12A7 transparent film to replace the expensive indium tin oxide transparent conductive film material, and at the same time uses the up (down) conversion luminescence properties of doped rare earth ions to limit the response of solar cells to sunlight. Extend to the full spectrum range and improve the photoelectric conversion efficiency of solar cells. Therefore, the design of RE:C12A7 transparent conductive film can achieve the purpose of simplifying the structure of the solar cell and reducing the cost while improving the photoelectric conversion efficiency of the solar cell.

Claims (1)

1. a preparation method for rear-earth-doped C 12 A 7 thin-film material, is characterized in that this preparation method, specificallyPrepare according to following steps:

One, by CaO powder and Al₂O₃Powder mixes, then adds rare earth oxide, then grinds 5h, is mixedPowder, wherein the quality of CaO is 2.8g and Al₂O₃Quality be 2.9697g, Er in rare earth oxide₂O₃Quality be0.0080g，Yb₂O₃Quality be 0.0820g;

Two, mixed-powder step 1 being obtained, is under 15MPa condition at pressure, and pressurize 5min, is pressed into material piece;

Three, material piece step 2 being obtained is sintering under air atmosphere, and controlling sintering temperature is 1300 DEG C, and sintering time is11h, obtains rear-earth-doped C 12 A 7 polycrystalline material;

Four, the rear-earth-doped C 12 A 7 polycrystalline material that adopts magnetron sputtering method that step 3 is obtained is splashed to substrate surfaceUpper, sputtering parameter is: be evacuated to 9.0 × 10^-4Pa, control sputtering pressure is 5Pa, substrate temperature is 300 DEG C, radio frequency electricalSource sputtering power is 100W, and sputtering time is 120min, and argon flow amount is 40sccm, then the film that substrate surface is obtainedMaterial reduces post processing, makes rear-earth-doped C 12 A 7 thin-film material; Wherein, in step 4, substrate is glassOr silicon chip, described glass is quartz glass; Described rear-earth-doped C 12 A 7 polycrystalline material is that erbium, ytterbium pair mix sevenAluminic acid ten dicalcium polycrystalline materials, wherein mole doping content of erbium ion is 1%, mole doping content of ytterbium ion is 10%.