CN103367125A - Method for improving diffusion quality by changing polycrystalline silicon slice phosphorus source components - Google Patents
Method for improving diffusion quality by changing polycrystalline silicon slice phosphorus source components Download PDFInfo
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- CN103367125A CN103367125A CN2013103021452A CN201310302145A CN103367125A CN 103367125 A CN103367125 A CN 103367125A CN 2013103021452 A CN2013103021452 A CN 2013103021452A CN 201310302145 A CN201310302145 A CN 201310302145A CN 103367125 A CN103367125 A CN 103367125A
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Abstract
The invention discloses a method for improving diffusion quality by changing polycrystalline silicon slice phosphorus source components, and relates to the technical field of methods for manufacturing semiconductor devices. The method includes the following steps that (1) phosphorus trichloride is added in phosphorus oxychloride and used as a phosphorus source; (2) oxidization: polycrystalline silicon slices with the manufactured suede are placed in a diffusion furnace, and oxygen is added in the diffusion furnace; (3) deposition: mixed gas of the phosphorus source and the oxygen is added in the diffusion furnace; (4) diffusion: the diffusion furnace is kept at a certain temperature, and then deposited phosphorus silicon slices are diffused in the diffusion furnace. Through the method, the service life of minority carriers in the polycrystalline silicon slices is prolonged, the diffusion gettering effect is beneficially improved, damage to crystal lattices in the high temperature process is reduced, and then photoelectric conversion efficiency is improved.
Description
Technical field
The present invention relates to the manufacture method technical field of semiconductor device.
Background technology
The energy is basis and the prerequisite of all economic development activities of the world, and is in the epoch that this scientific and technological level is maked rapid progress, human more strong to demand and the degree of dependence of the energy.Will be exhausted after 60 years according to all explored reserves of oil amounts of the statistics whole world, the mankind will be faced with severe viability test when the time comes; And the financial crisis of global range this time, with energy factor also be closely bound up.Only have the utilization ratio of practical reinforcement exploitation regenerative resource and the raising energy, break away from the dependence to traditional energy, just can tackle the problem at its root.Have prophesy to claim the 4th time human scientific and technological revolution in world's financial crisis, to ferment, and new forms of energy will be the key breakthrough points of this revolution.Solar energy is inexhaustible clean energy resource, under the background of fossil energy with exhaustion, solar energy with its recyclability, spatter property, easily obtaining property, be not subjected to politics restricted, replace traditional energy and be thing sooner or later, so it utilizes prospect very bright.
It is exactly the solar panel that adopts based on photovoltaic effect that solar energy is the most directly utilized, and is converted into electric energy behind the absorption sunlight.Photoelectric conversion efficiency is to weigh one of most important index of solar cell quality parameter.Some developed country's suitability for industrialized production can reach more than 18% even 20%; The average conversion efficiency of solar cell of most domestic photovoltaic enterprise generally rests in 17%.For improving the utilization ratio of solar cell, farthest obtain energy from the sun, be necessary to study influencing factor and the improvement method thereof of solar cell conversion efficiency; Cost Problems is the basic factor that the restriction solar cell is applied at home in addition, adds the impact of global financial crisis, reduces the height that cost has risen to the enterprise operation development strategy.So how to reduce to greatest extent cost and be present stage each large manufacture of solar cells enterprise target of doing one's utmost to pursue.
The manufacturing process of polycrystalline silicon solar cell mainly comprises: making herbs into wool, diffusion, etching, plated film, printing and sintering etc.And PN junction is the heart of polycrystalline silicon solar cell, also is one of key of battery quality quality.Emitter region for the conventional silicon solar cell of n+/p generally is the shallow junction zone that diffuses to form by phosphorus, owing to being in the interstitial void position at diffusion region phosphorus, easily cause distortion of lattice, and owing to the atomic radius of P and Si does not mate, mismatch also easily appears, and therefore should the zone specific activity larger, easily attract impurity, can become the complex centre of minority carrier, thereby reduce minority carrier life time.
The diffusion technology that present solar energy industry generally adopts is a constant source diffusion (deposition) and restriction source diffusion (propelling).During diffusion for generate can with the phosphorus pentoxide of pasc reaction, when passing into phosphorus oxychloride, to pass into the oxygen of q.s, but in the oxygen atmosphere of high temperature, because the fault in material of polysilicon self, the oxidation stacking fault defect easily occurs, this defective very easily forms the complex centre, falls so that photo-generated carrier is all meaninglessly compound, causes decrease in efficiency.
Diffusion principle: with the liquid source bottle of protective gas (nitrogen) by constant temperature (bubbling or blow over the surface); impurity source steam is brought in the High temperature diffusion pipe; through high temperature thermal decomposition and silicon chip surface reaction; restore foreign atom; and to the silicon chip diffusion inside, thereby forming at the interface PN junction with P type silicon substrate.TongYuan's deposition: the source refers to phosphorus oxychloride, and the phosphorus oxychloride of carrying by nitrogen at a certain temperature generates phosphorus at the quartz ampoule internal reaction provides impurity source for diffusion, finally is deposited on the surface of polysilicon chip.Advance: do not pass at a certain temperature the foreign matter of phosphor that in the situation of phosphorus oxychloride back is deposited and further in silicon chip, spread so that the junction depth of control PN junction and impurity concentration gradient distribute.Stacking fault: common a kind of planar defect in the layer structure lattice.It is the crystal structure layer normal periodically repeating stacking sequence mistake occurred at certain two interlayer, thereby cause along both sides, this interlayer plane (being called the fault face) near the mistake of atom arrange.
Summary of the invention
Technical problem to be solved by this invention provides a kind of method that improves the diffusion quality by changing polysilicon chip phosphorus derived components, described method has improved the life-span of few son in the polysilicon chip, be conducive to promote the gettering effect of diffusion, reduce the lattice damage that pyroprocess is brought, and then improve photoelectric conversion efficiency.
For solving the problems of the technologies described above, the technical solution used in the present invention is: a kind of method that improves the diffusion quality by changing polysilicon chip phosphorus derived components is characterized in that may further comprise the steps:
(1) in phosphorus oxychloride, adds phosphorus trichloride as the phosphorus source;
(2) oxidation: the polysilicon chip that will make matte is placed on and passes into oxygen in the diffusion furnace;
(3) deposition: in diffusion furnace, pass into the mist that carries phosphorus source and oxygen;
(4) diffusion: diffusion furnace keeps uniform temperature, and the phosphorus of deposition is spread to silicon chip inside.
Further, described step (1) is specially: add the phosphorus trichloride of 1%-5% as the phosphorus source in phosphorus oxychloride.
Further, described step (2) is specially: the polysilicon chip that will make matte is placed in the diffusion furnace, and temperature stabilization passes into 5-10min oxygen in the time of 800-900 ℃ in boiler tube, and speed is 500-2000 sccm.
Further, described step (3) is specially: TongYuan's deposition, pass into the nitrogen that carries the phosphorus source, and speed is 500-2000sccm and oxygen, and speed is the mist of 300-1000sccm, and sedimentation time is 10-20min.
Further, described step (4) is specially: diffusion furnace keeps 800-900 ℃ temperature, continues 10-15min, and the phosphorus of deposition is spread to silicon chip inside.
The beneficial effect that adopts technique scheme to produce is: under hot conditions, phosphorus oxychloride is decomposed into phosphorus pentachloride and phosphorus pentoxide, phosphorus pentachloride and oxygen reaction generate phosphorus pentoxide and chlorine, phosphorus pentoxide can be directly and pasc reaction generate silicon dioxide and elemental phosphorous, the phosphorus trichloride and the chlorine reaction that add in the phosphorus source have generated phosphorus pentachloride, can continue to react with oxygen.In addition, because the intermediate product phosphorus pentachloride of diffusion reaction has corrosiveness to silicon chip, before deposition step, increase the oxidation link, generate layer of oxide layer by oxidation at silicon chip surface, play the protective effect to silicon chip.
In the conventional diffusion technology process, because the time is longer, the surface can constantly have the phosphorus diffuse elements to enter, under high-temperature condition, P elements constantly is pushed into again below the silicon chip top layer, and silicon chip surface has a large amount of P elements and is enriched in this as a transition zone, cause this place can produce distortion and the dislocation of some lattices, thereby produce high recombination region.In new method of diffusion of the present invention, by in phosphorus oxychloride, adding phosphorus trichloride, increased the content of chlorine in the diffusion reaction, the existence of chlorine can effectively hinder the generation of stacking fault, improves the diffusion quality, simultaneously, chlorine can generate metal complex and take diffusion furnace out of with the gas in the diffusion furnace tube with the metal ion reaction, has improved the minority carrier life time of silicon chip, is conducive to promote the gettering effect of diffusion, reduce the lattice damage that pyroprocess is brought, and then improve photoelectric conversion efficiency.Through the test of quasi-stable state photoconductive method, under the conventional diffusion technology, the minority carrier life time of silicon chip is 8 microseconds, and the minority carrier life time of new diffusion technology lower silicon slice can reach 9 microseconds.
Embodiment
Have the defective that easily causes the oxidation stacking fault for existing diffusion technology, proposed to change the novel diffusion way of existing conventional phosphoric diffusion technology and phosphorus derived components, embodiment is as follows:
Embodiment one: a kind of method that improves the diffusion quality by changing polysilicon chip phosphorus derived components may further comprise the steps:
(1): the phosphorus trichloride of adding 1% is as the phosphorus source in phosphorus oxychloride.
(2): the polysilicon chip that will make matte is placed in the diffusion furnace, and temperature stabilization passes into 5min oxygen in the time of 800 ℃ in boiler tube, and speed is 500sccm.
(3): TongYuan's deposition, pass into the nitrogen that carries the phosphorus source, speed is 500sccm and oxygen, and speed is the mist of 300sccm, and sedimentation time is 10min.
(4): diffusion furnace keeps 800 ℃ temperature, continues 10min, and the phosphorus of deposition is spread to silicon chip inside.
Through the test of quasi-stable state photoconductive method, the minority carrier life time of silicon chip can reach 9 microseconds.
Embodiment two: a kind of method that improves the diffusion quality by changing polysilicon chip phosphorus derived components may further comprise the steps:
(1): the phosphorus trichloride of adding 3% is as the phosphorus source in phosphorus oxychloride.
(2): the polysilicon chip that will make matte is placed in the diffusion furnace, and temperature stabilization passes into 8min oxygen in the time of 850 ℃ in boiler tube, and speed is 1500 sccm.
(3): TongYuan's deposition, pass into the nitrogen that carries the phosphorus source, speed is 1500sccm and oxygen, and speed is the mist of 700sccm, and sedimentation time is 15min.
(4): diffusion furnace keeps 850 ℃ temperature, continues 13min, and the phosphorus of deposition is spread to silicon chip inside.
Through the test of quasi-stable state photoconductive method, the minority carrier life time of silicon chip can reach 9 microseconds.
Embodiment three: a kind of method that improves the diffusion quality by changing polysilicon chip phosphorus derived components may further comprise the steps:
(1): the phosphorus trichloride of adding 5% is as the phosphorus source in phosphorus oxychloride.
(2): the polysilicon chip that will make matte is placed in the diffusion furnace, and temperature stabilization passes into 10min oxygen in the time of 900 ℃ in boiler tube, and speed is 2000 sccm.
(3): TongYuan's deposition, pass into the nitrogen that carries the phosphorus source, speed is 2000sccm and oxygen, and speed is the mist of 1000sccm, and sedimentation time is 20min.
(4): diffusion furnace keeps 900 ℃ temperature, continues 15min, and the phosphorus of deposition is spread to silicon chip inside.
Through the test of quasi-stable state photoconductive method, the minority carrier life time of silicon chip can reach 9 microseconds.1%-5% refers to the percentage of phosphorus trichloride and phosphorus oxychloride quality.
Under hot conditions, phosphorus oxychloride is decomposed into phosphorus pentachloride and phosphorus pentoxide, phosphorus pentachloride and oxygen reaction generate phosphorus pentoxide and chlorine, phosphorus pentoxide can be directly and pasc reaction generate silicon dioxide and elemental phosphorous, the phosphorus trichloride and the chlorine reaction that add in the phosphorus source have generated phosphorus pentachloride, can continue to react with oxygen.In addition, because the intermediate product phosphorus pentachloride of diffusion reaction has corrosiveness to silicon chip, before deposition step, increase the oxidation link, generated layer of oxide layer by oxidation at silicon chip surface, played the protective effect to silicon chip.
In the conventional diffusion technology process, because the time is longer, the surface can constantly have the phosphorus diffuse elements to enter, under high-temperature condition, P elements constantly is pushed into again below the silicon chip top layer, and silicon chip surface has a large amount of P elements and is enriched in this as a transition zone, cause this place can produce distortion and the dislocation of some lattices, thereby produce high recombination region.In new method of diffusion of the present invention, by in phosphorus oxychloride, adding phosphorus trichloride, increased the content of chlorine in the diffusion reaction, the existence of chlorine can effectively hinder the generation of stacking fault, improves the diffusion quality, simultaneously, chlorine can generate metal complex and take diffusion furnace out of with the gas in the diffusion furnace tube with the metal ion reaction, has improved the minority carrier life time of silicon chip, is conducive to promote the gettering effect of diffusion, reduce the lattice damage that pyroprocess is brought, and then improve photoelectric conversion efficiency.Through the test of quasi-stable state photoconductive method, under the conventional diffusion technology, the minority carrier life time of silicon chip is 8 microseconds, and the minority carrier life time of new diffusion technology lower silicon slice can reach 9 microseconds.
Used specific case herein principle of the present invention and execution mode thereof are set forth, the explanation of above embodiment is just with helping understand method of the present invention and core concept thereof.Should be pointed out that for the person of ordinary skill of the art, can also carry out some improvement and modification to the present invention under the prerequisite that does not break away from the principle of the invention, these improvement and modification also fall in the protection range of claim of the present invention.
Claims (5)
1. one kind is passed through to change the method that polysilicon chip phosphorus derived components improves the diffusion quality, it is characterized in that may further comprise the steps:
(1) in phosphorus oxychloride, adds phosphorus trichloride as the phosphorus source;
(2) oxidation: the polysilicon chip that will make matte is placed on and passes into oxygen in the diffusion furnace;
(3) deposition: in diffusion furnace, pass into the mist that carries phosphorus source and oxygen;
(4) diffusion: diffusion furnace keeps uniform temperature, and the phosphorus of deposition is spread to silicon chip inside.
2. a kind of method that improves the diffusion quality by changing polysilicon chip phosphorus derived components according to claim 1 is characterized in that described step (1) is specially: add the phosphorus trichloride of 1%-5% as the phosphorus source in phosphorus oxychloride.
3. according to claim 1 a kind of by changing the method for polysilicon chip phosphorus derived components raising diffusion quality, it is characterized in that described step (2) is specially: the polysilicon chip that will make matte is placed in the diffusion furnace, temperature stabilization is in the time of 800-900 ℃ in boiler tube, pass into 5-10min oxygen, speed is 500-2000 sccm.
4. according to claim 1 a kind of by changing the method for polysilicon chip phosphorus derived components raising diffusion quality, it is characterized in that described step (3) is specially: TongYuan's deposition, pass into the nitrogen that carries the phosphorus source, speed is 500-2000sccm and oxygen, speed is the mist of 300-1000sccm, and sedimentation time is 10-20min.
5. according to claim 1 a kind of by changing the method for polysilicon chip phosphorus derived components raising diffusion quality, it is characterized in that described step (4) is specially: diffusion furnace keeps 800-900 ℃ temperature, continue 10-15min, the phosphorus of deposition is spread to silicon chip inside.
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| CN103130179A (en) * | 2011-12-02 | 2013-06-05 | 横河电机株式会社 | Method of manufacturing resonant transducer |
| CN103178157A (en) * | 2013-02-27 | 2013-06-26 | 苏州阿特斯阳光电力科技有限公司 | Method for manufacturing polycrystalline silicon solar cells with selective emitters |
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| US4806499A (en) * | 1985-06-13 | 1989-02-21 | Oki Electric Industry Co., Ltd. | Method of manufacturing Bi-CMOS semiconductor IC devices using dopant rediffusion |
| CN86104069A (en) * | 1986-06-09 | 1987-02-11 | 电子工业部第四十四研究所 | The multiple impurity-absorbing technique of silicon and multiple impurity-absorbed silicon slice |
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Application publication date: 20131023 |