CN101724901B - Method for preparing aluminum-induced crystallized polycrystalline silicon film in hydrogen plasma atmosphere - Google Patents
Method for preparing aluminum-induced crystallized polycrystalline silicon film in hydrogen plasma atmosphere Download PDFInfo
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- CN101724901B CN101724901B CN2009102448454A CN200910244845A CN101724901B CN 101724901 B CN101724901 B CN 101724901B CN 2009102448454 A CN2009102448454 A CN 2009102448454A CN 200910244845 A CN200910244845 A CN 200910244845A CN 101724901 B CN101724901 B CN 101724901B
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Abstract
The invention discloses a method for preparing an aluminum-induced crystallized polycrystalline silicon film in a hydrogen plasma atmosphere, which comprises the following steps: depositing multiplayer films comprising an amorphous silicon film, a silicon dioxide film and an aluminum metal film on a substrate, and annealing the multiplayer films at the temperature of between 450 and 550 DEG C in the hydrogen plasma atmosphere to obtain fully-crystallized polycrystalline silicon film in short time. The method not only combines the traditional annealing crystallization process and the hydrogen plasma crystallization and passivation process together, but also reduces the annealing time of aluminum-induced crystallization, reduces the thermal budget and can remarkably reduce the cost; the polycrystalline silicon film material prepared through the aluminum-induced crystallization in the hydrogen plasma atmosphere can be used for preparing devices such as low-temperature polycrystalline silicon film transistors in polycrystalline silicon film solar cells and flat displays and the like; and the method has the characteristics of simplified process, little thermal budget, low cost and the like, and is a crystallization method suitable for industrially producing the polycrystalline silicon film material in large scale.
Description
[technical field]
The invention belongs to the technology of preparing of polycrystalline silicon film material, the preparation method of aluminum-induced crystallized polycrystalline silicon film in particularly a kind of hydrogen plasma atmosphere.
[background technology]
Polysilicon membrane; Has lower cost with respect to silicon single crystal; Have higher mobility and stability with respect to amorphous silicon membrane, it is just attracting the very big concern of scientific circles in the large area electron device wide application prospect in solar cell, thin film transistor, the transmitter particularly.Regrettably; The technology of preparing of polysilicon membrane all has its limitation separately at present: thus the film of the method that has preparation is because grain-size is less or the relatively poor electric property of homogeneity is not good enough; As plasma reinforced chemical vapour deposition (Plasma Enhanced ChemicalVapor Deposition---the PECVD) microcrystalline silicon film of low temperature preparation, its grain-size and mobility can not show a candle to the silicon film of polycrystalline structure; Other; As low-pressure chemical vapor deposition (Low Pressure ChemicalVapor Deposition---LPCVD); (Atmospheric PressureChemical Vapor Deposition---APCVD), solid phase crystallization (Solid PhaseCrystallization---SPC) etc. needs higher crystallization temperature to aumospheric pressure cvd; PRK crystallization (Excimer Laser Annealing ELA) for another example, and rapid thermal annealing (Rapid Thermal Annealing---RTA) wait then apparatus expensive.The metal-induced crystallization technology is to utilize combining of non-crystalline silicon and some metal (like Ni, Al, Cu etc.); Thereby reduce its crystallization temperature and can realize the low temperature preparation; It has that technology is simple, cost is low and characteristics such as annealing process is short, makes it be more suitable for being applied to industrial production.Wherein, Aluminum-induced crystallized can not only be at low temperature (below 600 degrees centigrade) complete crystallization amorphous silicon membrane; And the polysilicon of preparation also has the advantage of big crystal grain and 100 preferred orientations; Suitable to especially inculating crystal layer low-temperature epitaxy growth polysilicon, this technology is widely used in polysilicon solar cell.Regrettably, even aluminum-induced crystallized under lower temperature, annealing still needs long annealing time, be unfavorable for the industrialization of polysilicon solar cell and polycrystalline SiTFT substrate.In addition, the crystal boundary of the polysilicon membrane after crystallization and crystal grain inside are contained higher defect state usually, have a strong impact on the performance and the stability of polysilicon membrane and device.Then hydrogen treatment is one of effective ways of passivation polysilicon film device defect state, and method commonly used is that polysilicon membrane is annealed under the atmosphere of hydrogen plasma.
[summary of the invention]
The objective of the invention is to above-mentioned existing problems; The preparation method of aluminum-induced crystallized polycrystalline silicon film in a kind of hydrogen plasma atmosphere is provided, and this method utilizes plasma body to reduce aluminum-induced crystallized temperature, shortens the time of realizing the complete crystallization process; Realize aluminum-induced crystallized annealing and post-passivation synchronously; Improve the aluminum-induced crystallized polycrystalline silicon film quality, reduce the energy waste and the cost of preparation process, for a new road is opened up in the preparation of polysilicon membrane.
Technical scheme of the present invention:
The preparation method of aluminum-induced crystallized polycrystalline silicon film in a kind of hydrogen plasma atmosphere, step is following:
1) deposition comprises that amorphous silicon membrane, silica membrane and metallic aluminium film make multilayer film on substrate;
2) above-mentioned multilayer film are put into lehre, lehre is vacuumized and lehre is warming up to annealing temperature;
3) feed hydrogen and produce hydrogen plasma, multilayer film are exposed in the hydrogen plasma atmosphere through the hydrogen plasma generation source that is arranged in the lehre;
4) under lehre homo(io)thermism condition, anneal;
5) close hydrogen gas plasma the source takes place, stop logical hydrogen, secondary vacuum pumping is treated from lehre, to take out after the nature cooling, can make the polycrystalline silicon film material of complete crystallization.
Vacuum tightness in the said lehre is (200～800) * 10
-3Torr.
Said annealing temperature is 450 ℃～550 ℃.
Said hydrogen plasma generation source is radio frequency glow discharge, ultra-high frequency photoglow, microwave-excitation, heat is auxiliary or the short range or the long-range hydrogen plasma source of the generation of heated filament decomposition method.
Said hydrogen flowing quantity is 15sccm～60sccm.
Said annealing time is for being no less than 2 hours.
Advantage of the present invention and effect: the present invention carries out aluminum-induced crystallized annealing process in the atmosphere of hydrogen plasma, and traditional annealing and back hydrogenation process are united two into one, and has simplified technology, has reduced cost; In annealing process; Wasserstoffatoms in the hydrogen plasma can be in the annealing time shorter than the conventional aluminum revulsive crystallization crystallizing amorphous silicon film; Utilize hydrogen plasma atmosphere to quicken aluminum-induced crystallized annealing process, can reduce aluminum-induced crystallized annealing time effectively; The present invention is through the polycrystalline silicon film material of the aluminum-induced crystallized preparation of hydrogen plasma atmosphere; Can be used for preparing the devices such as low-temperature polysilicon film transistor in polysilicon thin-film solar battery, the flat-panel display device; Having characteristics such as work simplification, heat budget is few, cost is low, is a kind of crystallization method that is applicable to the polycrystalline silicon film material of large-scale commercial prodn.
[description of drawings]
Fig. 1 a prepares amorphous silicon membrane, silica membrane and aluminium film three-decker film schematic cross-section successively on the substrate.
Fig. 1 b prepares aluminium film, silica membrane and amorphous silicon membrane three-decker film schematic cross-section successively on the substrate.
Fig. 2 is thin 550 ℃ of annealing times of the aluminum-induced crystallized polycrystalline silicon of embodiment 1 preparation and silicon film crystallization rate corresponding relation figure.
Fig. 3 is thin 550 ℃ of annealing times of the aluminum-induced crystallized polycrystalline silicon of embodiment 2 preparations and silicon film crystallization rate corresponding relation figure.Among the figure: 1. substrate 2. amorphous silicon membranes 3. silica membranes 4. aluminium films
[embodiment]
Embodiment 1:
The preparation method of aluminum-induced crystallized polycrystalline silicon film in a kind of hydrogen plasma atmosphere, step is following:
1) on large-area glass substrate 1; Adopt the method for low-pressure chemical vapor deposition (LPCVD),, from the preparation chamber, take out amorphous silicon membrane at 550 ℃ of amorphous silicon membrane layers 2 that deposit 100nm is thick; Natural oxidation in air; The silica membrane 3 that its surface forms a layer thickness 3nm adopts the method for vacuum-evaporation on amorphous silicon layer, to form the thick aluminium film 4 of 100nm then, and its structure is shown in Fig. 1 a;
2) above-mentioned multilayer film are put into lehre, lehre adopts radio frequency glow discharge short range hydrogen plasma equipment, and lehre is evacuated to 100 * 10
-6Below the torr, lehre is warming up to 550 degrees centigrade;
3) feed hydrogen, flow is 30sccm, and chamber vacuum is adjusted into 800 * 10
-3Torr opens radio frequency (RF) power supply, and power setting is 30W, and substrate/amorphous silicon/silicon dioxide/aluminium multilayer film will be exposed in the plasma body this moment;
4) under lehre homo(io)thermism condition, annealed 4 hours;
5) close hydrogen gas plasma the source takes place, stop logical hydrogen, be evacuated to 100 * 10
-6Below the torr, treat from lehre, to take out after the nature cooling, can make the polycrystalline silicon film material of complete crystallization.
Technique effect detects: with the above-mentioned polycrystalline silicon film material that makes with 85% phosphoric acid dip 10 minutes; Clean up at the residual aluminium of silicon film surface; Use Raman spectrogram that model records film as Raman (Raman) spectrograph of Renishaw in Via through 520,510,480 3 these matches of peak height, with formula Xc=(I
520+ I
510)/(I
520+ I
510+ I
480) calculating the silicon film crystallization rate, the 4 hours crystallization rates that obtain under hydrogen plasma atmosphere, annealing are 100%, promptly make the polysilicon membrane of complete crystallization.Shown in Figure 2 is substrate/amorphous silicon/silicon dioxide/aluminium multilayer film under hydrogen plasma atmosphere with vacuum under the corresponding relation figure of annealing time and crystallization rate; Compare with the polysilicon membrane of the ability acquisition in 10 hours of annealing under vacuum condition complete crystallization; Show that this method can reduce aluminum-induced crystallized annealing time, reduce heat budget.
Embodiment 2:
The preparation method of aluminum-induced crystallized polycrystalline silicon film in a kind of hydrogen plasma atmosphere, step is following:
1) on large-area glass substrate 1; Adopt the method for vacuum-evaporation on amorphous silicon layer, to form the thick aluminum film layer of 100nm 4; The thick silica membrane layer 3 of method deposition 10nm of using plasma chemical vapour deposition (PECVD); Adopt the method for low-pressure chemical vapor deposition (LPCVD) again, at 550 ℃ of amorphous silicon membrane layers 2 that deposit 100nm is thick, its structure is shown in Fig. 1 b;
2) above-mentioned multilayer film are put into lehre, lehre adopts radio frequency glow discharge short range hydrogen plasma equipment, and lehre is evacuated to 100 * 10
-6Below the torr, lehre is warming up to 450 degrees centigrade;
3) feed hydrogen, flow is 15sccm, and cavity air pressure is adjusted into 200 * 10
-3Torr opens radio frequency (RF) power supply, and power setting is 10W, and substrate/aluminium/silicon-dioxide/non-crystalline silicon multilayer film will be exposed in the plasma body this moment;
4) under lehre homo(io)thermism condition, annealed 5 hours;
5) close hydrogen gas plasma the source takes place, stop logical hydrogen, be evacuated to 100 * 10
-6Below the torr, treat from lehre, to take out after the nature cooling, can make the polycrystalline silicon film material of complete crystallization.
Technique effect detects: the phosphoric acid dip with 85% 10 minutes; Clean up at the residual aluminium of silicon film surface; Use Raman spectrogram that model records film as Raman (Raman) spectrograph of Renishaw in Via through 520,510,480 3 these matches of peak height, with formula Xc=(I
520+ I
510)/(I
520+ I
510+ I
480) calculating the silicon film crystallization rate, the 5 hours crystallization rates that obtain under hydrogen plasma atmosphere, annealing are 100%, promptly make the polysilicon membrane of complete crystallization.Shown in Figure 2 is substrate/aluminium/silicon-dioxide/non-crystalline silicon multilayer film under hydrogen plasma atmosphere with vacuum under the corresponding relation figure of annealing time and crystallization rate; Compare with the polysilicon membrane of the ability acquisition in 13 hours of annealing under vacuum condition complete crystallization; Show that this method can reduce aluminum-induced crystallized annealing time, reduce heat budget.
Claims (5)
1. the preparation method of aluminum-induced crystallized polycrystalline silicon film in the hydrogen plasma atmosphere is characterized in that step is following:
1) deposition comprises that amorphous silicon membrane, silica membrane and metallic aluminium film make multilayer film on substrate;
2) above-mentioned multilayer film are put into lehre, lehre is vacuumized and lehre is warming up to annealing temperature;
3) feed hydrogen and produce hydrogen plasma, multilayer film are exposed in the hydrogen plasma atmosphere through the hydrogen plasma generation source that is arranged in the lehre;
4) under lehre homo(io)thermism condition, anneal;
5) close hydrogen plasma the source takes place, stop logical hydrogen, secondary vacuum pumping is treated from lehre, to take out after the nature cooling, can make the polycrystalline silicon film material of complete crystallization.
2. according to the preparation method of aluminum-induced crystallized polycrystalline silicon film in the said hydrogen plasma atmosphere of claim 1, it is characterized in that: said annealing temperature is 450 ℃～550 ℃.
3. according to the preparation method of aluminum-induced crystallized polycrystalline silicon film in the said hydrogen plasma atmosphere of claim 1, it is characterized in that: said hydrogen plasma generation source is short range or the long-range hydrogen plasma source that radio frequency glow discharge, microwave-excitation or hot householder method produce.
4. according to the preparation method of aluminum-induced crystallized polycrystalline silicon film in the said hydrogen plasma atmosphere of claim 1, it is characterized in that: the flow of said hydrogen is 15sccm～60sccm.
5. according to the preparation method of aluminum-induced crystallized polycrystalline silicon film in the said hydrogen plasma atmosphere of claim 1, it is characterized in that: the said annealed time is for being no less than 2 hours.
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102010062386B4 (en) | 2010-12-03 | 2014-10-09 | Evonik Degussa Gmbh | Method for converting semiconductor layers, semiconductor layers produced in this way, and electronic and optoelectronic products comprising such semiconductor layers |
| DE102010062383A1 (en) | 2010-12-03 | 2012-06-06 | Evonik Degussa Gmbh | Method for converting semiconductor layers |
| CN102709404A (en) * | 2012-06-21 | 2012-10-03 | 上海大学 | Method for preparing polycrystalline silicon film by carrying out induced crystallization on amorphous silicon film by using metallic copper under low temperature |
| CN102789989A (en) * | 2012-08-15 | 2012-11-21 | 京东方科技集团股份有限公司 | Polycrystalline silicon transistor, display device and manufacturing method of polycrystalline silicon transistor |
| CN103311105A (en) * | 2013-05-16 | 2013-09-18 | 上海大学 | Method for inducing crystallization of amorphous silicon thin film into polycrystalline silicon thin film by aluminum at low temperature |
| CN103985637B (en) * | 2014-04-30 | 2017-02-01 | 京东方科技集团股份有限公司 | Low-temperature polycrystalline silicon thin film transistor, manufacturing method thereof and display device |
| CN104975260B (en) * | 2015-08-05 | 2018-05-01 | 大连大学 | A kind of preparation method of high crystallization rate polysilicon membrane |
| CN106835289A (en) * | 2016-12-30 | 2017-06-13 | 武汉华星光电技术有限公司 | A kind of device and method for preparing low temperature polycrystalline silicon |
| CN109943823A (en) * | 2019-03-07 | 2019-06-28 | 上海米蜂激光科技有限公司 | The method for preparing a-Si:H film based on hydrogen plasma process |
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| CN1727525A (en) * | 2005-03-04 | 2006-02-01 | 中国科学院长春光学精密机械与物理研究所 | A kind of method for preparing polysilicon |
| CN100999388A (en) * | 2006-12-30 | 2007-07-18 | 南开大学 | Preparation method of polycrystalline silicon film of decorated and coated solution on surface with induction crystallization |
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| CN1727525A (en) * | 2005-03-04 | 2006-02-01 | 中国科学院长春光学精密机械与物理研究所 | A kind of method for preparing polysilicon |
| CN100999388A (en) * | 2006-12-30 | 2007-07-18 | 南开大学 | Preparation method of polycrystalline silicon film of decorated and coated solution on surface with induction crystallization |
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