CN102842492A - Crystal silicon laser-assisted aluminum-boron co-doping and electrode preparation method - Google Patents
Crystal silicon laser-assisted aluminum-boron co-doping and electrode preparation method Download PDFInfo
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Abstract
A crystal silicon laser-assisted aluminum-boron co-doping and electrode preparation method is characterized in that technical methods such as a magnetron sputtering method, an electron beam evaporation method, a silk screen printing method and the like are adopted to prepare a layer of aluminum-boron film layer on the surface of crystalline silicon, wherein the content of boron is 0.001 percent by weight to 5 percent by weight and is preferably 0.05 percent by weight to 1 percent by weight; and then laser is used for radiating the aluminum-boron film layer so as to smelt the aluminum-boron film, and the silicon below the aluminum-boron film is also smelted to form an aluminum-boron-silicon co-smelt body. When the power supply of the laser is cut off or the laser is moved away, the area is rapidly cooled, the silicon is separated out from the co-smelt body to be crystallized and grown, partial aluminum atoms and boron atoms remain in the crystalline silicon, so that the aluminum-boron co-doping of the crystalline silicon is realized, residual aluminum and boron are solidified on the surface of the area to form a film, and the film is contacted with the aluminum-boron film layer which is not radiated by the laser to form an electrode. Compared with traditional methods reported in the literatures, the method has characteristics of high stability and simple process.
Description
Technical field
The invention belongs to semi-conducting material and device technology field,, relate to a kind of method of two kinds of element codopes of laser technology realization aluminium boron and preparation method of related electrode thereof of adopting in the crystalline silicon particularly based on the technical field of electronic devices of crystal silicon semiconductor.
Technical background
Crystalline silicon is current most widely used semi-conducting material, has critical role in technical fields such as various microelectronic components (like MOS, MOSFET, MESFET etc.), opto-electronic device (like light-emitting diode, solar cell, laser, photo-detector etc.) and power electronic devices.The technical matters of silicon materials is very ripe, industrial chain is complete, cost is relatively low, and reserves are abundant, will be most important semi-conducting material in future therefore.
Si semiconductor free from foreign meter or that impurity content is very low is called intrinsic semiconductor; The intrinsic semiconductor carrier concentration is low, resistivity is high; Its electrical property receives factor affecting such as temperature very big, therefore when the preparation electronic device, need it be mixed, and the semiconductor of doping often is called extrinsic semiconductor.When in the intrinsic silicon semiconductor, mixing a certain amount of the 3rd major element such as boron (B), aluminium (Al), gallium foreign atoms such as (Ga); Intrinsic silicon promptly becomes the p N-type semiconductor N, and its charge carrier mainly is the hole, along with the increase of doping content; Hole concentration improves rapidly, and resistivity reduces fast.If when in the intrinsic silicon semiconductor, mixing a certain amount of the 5th major element such as phosphorus (P), arsenic (Al), antimony foreign atoms such as (Sb); Intrinsic silicon promptly becomes the n N-type semiconductor N; Its charge carrier mainly is a free electron; Along with the increase of doping content, free electronic concentration improves rapidly, and resistivity reduces fast.If doping content is higher, this doped semiconductor is also referred to as n+ type or p+ N-type semiconductor N.
If the zones of different on a crystal silicon chip has the doping of control; Can obtain different types of basic devices such as p-n, p-n-p, p-n-p-n, n-p-n; These basic size of devices are controlled with arranging be connected, promptly can be made into large scale integrated circuit.Opto-electronic device generally is based on p-n junction and processes, and is actually the very p-n junction of big (being whole silicon wafer) of an area such as crystal silicon solar energy battery.
The doping of Si semiconductor generally is to realize through elevated temperature heat diffusion, can about 850 ℃ realize generally that such as the diffusion of phosphorus the diffusion of boron then need realize that about 1000 ℃ the high-temperature process of silicon chip often causes the decline of its electrical property.The doping of aluminium in silicon usually is through forming aluminium silicon eutectic in when heating between aluminium and the silicon, and the silicon in the aluminium silicon eutectic is separated out crystalline growth when cooling then, and part aluminium is stayed and realized the doping of aluminium in silicon in the silicon crystal.
Aluminium and boron are the p type and mix in silicon, but their doping content in crystalline silicon has significant difference.The solid solubility of aluminium in crystalline silicon is very little, so the doping content of aluminium in crystalline silicon is lower, and its doping content is generally at 3 x 10
18Atoms/cm
3In, and therefore the solid solubility of boron in crystalline silicon can realize the doping of higher concentration than more than high 1 one magnitude of aluminium.Yet as previously mentioned, boron needs very high temperature through the doping that thermal diffusion is implemented in the crystalline silicon, and this has restricted its range of application in silica-based electronic device preparation technology.
Laser supplementary doping technology has obtained fast development in recent years, generally adopt pulsed laser technique, can produce high temperature at regional area in the utmost point short time, and other zone then is not affected.The doping content that adopts laser supplementary doping technology can obtain to reach than routine techniques is higher.
Elements such as the doped chemical commonly used of crystalline silicon such as boron, aluminium, phosphorus all can mix through the local that laser technology is implemented in the crystalline silicon; Concrete technical method is narrated as follows: (1) applies the rete of one deck boracic or phosphorus at silicon chip surface; Mixing for aluminium, generally is with vacuum method deposition layer of metal aluminum membranous layer; (2) with the rete of pulsed laser irradiation silicon chip surface; Laser makes the silicon fusing of irradiation zone, and its depth of fusion can be regulated through the technological parameter of laser, and atom and silicon melt in the rete become eutectic; After laser is cut off power supply or removes; This eutectic is cooled off rapidly, and silicon is separated out and begun crystalline growth fast from this eutectic, and the part foreign atom rests in the silicon crystal of growth and realizes mixing.
Crystalline silicon laser auxiliary aluminum is mixed and has in fact also been accomplished the preparation of electrode; This is because vacuum-deposited layer of metal aluminum membranous layer has excellent conducting performance; Simultaneously directly forming ohm-type with local aluminium doped region electrically contacts; Therefore become the electrode of silica-based electronic device, like this, doping process and technology for preparing electrode can be accomplished in a step.And for boron or the laser supplementary doping of phosphorus in crystalline silicon; After laser doping is handled; Need the rete of boracic or phosphorus be washed from silicon chip, and then adopt the vacuum technique depositing metal membrane layer, this metallic diaphragm and boron or phosphorus doping zone form ohm-type and electrically contact; Thereby become electrode, obviously doping process and technology for preparing electrode are accomplished through two step process in this technology.
Though aluminium doping process and technology for preparing electrode can be accomplished in a step; But as previously mentioned, the doping content of aluminium in crystalline silicon is lower, therefore mixes for the p type that obtains higher concentration in the crystalline silicon; Be necessary simultaneously boron to be mixed; Realize the effect of aluminium boron codope,, therefore can obtain the p type doping effect of crystalline silicon middle and high concentration because boron is more much higher than aluminium in the doping content of crystalline silicon.Both at home and abroad about adopting laser technology to realize that the research report of aluminium boron codope in the crystalline silicon is few; One piece of research paper (M. Tucci etc. that delivered in 2009 by people such as Italian scientific research personnel Tucci is only arranged at present; Bragg reflector and laser fired back contact in a-Si:H/c-Si heterostructure solar cell, Materials Science and Engineering B, 2009; The 159-160 volume; The 48-52 page or leaf), they have reported the method that realizes the aluminium boron codope with the laser doping technology, and this method specifically describes as follows:
(1) with plasma reinforced chemical vapour deposition technology (PECVD) at p type monocrystalline silicon sheet surface deposition of amorphous silicon (a-Si:H) film as passivating film, deposited silicon nitride (SiN then
x) film, this a-Si:H/SiN
xComposite passivation film has excellent electric passivation to crystal silicon thin film
(2) with the doping liquid of spin-coating method spin coating one deck boracic on above-mentioned surface,, form boron doping rete then 250 ℃ of oven dry 15 minutes;
(3) the deposited by electron beam evaporation technology deposits the metallic aluminium rete of 2 μ m thickness on above-mentioned surface;
(4) use wavelength to shine above-mentioned metallic aluminium rete as the Q switching Nd:YAG pulse laser of 1064nm; The silicon of laser beam rapid deposite metal aluminium and its underpart forms aluminium silicon eutectic at this regional area; Boron in simultaneously above-mentioned (2) the step boron-dopped layer also is melted and is incorporated in the aluminium silicon eutectic, and after laser was cut off power supply or removes, local temperature reduced rapidly; Silicon is separated out from this eutectic and crystalline growth, realizes the aluminium boron codope in the crystalline silicon.Here only it should be noted that and above-mentioned fusing and doping process just take place, and in the non-irradiated zone of laser beam, each rete has no physics or chemical change in the zone of laser beam irradiation;
(5) accomplish doping process and technology for preparing electrode.
Obviously, there is following technical disadvantages in the method that the people proposed such as Tucci:
(1) technology is complicated, has comprised two kinds of boron doping rete and the metallic aluminium retes of boracic during preparation doping rete;
(2) boron doping rete after oven dry generally with B
2O
3Material is main content, and this rete is in the below of metal aluminium electrode, and B
2O
3Very easily thereby the moisture absorption loses chemical stability and structural intergrity, has a strong impact on the stability of its upper metal aluminium electrode and reduces the adhesive force of aluminium electrode, and therefore the silica-based electronic device by this method preparation is very unsettled.
The present invention is directed to the above-mentioned technical disadvantages of the crystalline silicon laser auxiliary aluminum boron codope technology of at present having reported both at home and abroad; Proposed a kind of in crystalline silicon a step accomplish laser auxiliary aluminum boron codope and electrode fabrication method; Prepared electrode has the high characteristics of stability, helps the excellent silica-based electronic device of obtained performance.
Summary of the invention
The objective of the invention is in order to adopt laser technology step in crystalline silicon to accomplish the technology of aluminium boron codope and electrode preparation; And simultaneously an amount of boron is mixed in the process of proposition preparation aluminum membranous layer on surface of crystalline silicon; That is preparation aluminium boron film layer; Wherein the content of boron is lower, is 0.001wt%-5wt%, preferred 0.05wt%-1wt%.When this aluminium boron film layer of laser beam irradiation; The aluminium boron film layer region that laser beam shone melts rapidly; Should also melt immediately by the beneath silicon in zone simultaneously; Aluminium, boron, the silicon three of fusing form eutectic, and the power of laser beam and pulse frequency have been confirmed the degree of depth of silicon melting range, are not excited then no change of light-struck zone.After laser is cut off power supply or removes; Cool off rapidly in this zone; Silicon is separated out the beginning crystalline growth from this eutectic, part aluminium atom and boron atom are stayed in this silicon metal, thereby realizes the aluminium boron codope of crystalline silicon; Remaining aluminium and boron will be in this regional surface solidification film forming, and are not excited light-struck aluminium boron film layer with other and are in contact with one another the formation electrode.
Fig. 1 shows method step of the present invention, and concrete steps are narrated as follows:
1. adopt the surface preparation aluminium boron film layer (referring to Fig. 1 b) of technical methods such as magnetron sputtering method, electron-beam vapor deposition method or silk screen print method at crystalline silicon, wherein the content of boron is 0.001wt%-5wt%, preferred 0.05wt%-1wt%.
2. adopt pulsed laser irradiation aluminium boron film layer (referring to Fig. 1 c), laser beam can be done linear scan irradiation or single-point type irradiation.The aluminium boron film layer in laser radiation zone at first melts, and also fusing immediately of the silicon of its bottom then forms aluminium, silicon, boron eutectic, and the degree of depth of melting range is by laser power, lasing beam diameter, and pulse frequency decision.
3. Laser Power Devices are cut off or laser is removed; Formed aluminium, silicon, boron eutectic are cooled off rapidly in the 2nd step; Silicon begins from this eutectic, to separate out and crystalline growth, and part aluminium atom and boron atom are stayed in this silicon metal, thereby realizes the aluminium boron codope of crystalline silicon; Remaining aluminium and boron will be in this regional surface solidification film forming, and are not excited light-struck aluminium boron film layer with other and are in contact with one another the formation electrode.
It is to be noted; In above-mentioned the 1st step; Before preparation aluminium boron film layer; Surface of crystalline silicon also can deposit the oxide or the nitride passivating film of skim (like 80nm thickness) earlier with plasma enhanced chemical vapor deposition technology (PECVD, Plasma enhanced chemical vapor deposition), and then at its surface preparation aluminium boron film layer (seeing shown in Figure 2).
The invention has the beneficial effects as follows: compare with the crystalline silicon laser auxiliary aluminum boron codope method of reporting in the existing document; Method proposed by the invention does not need one deck boron doping rete; Do not use the boron compound of boron oxide compound or other kind; Therefore the present invention will be not because of the technical disadvantages of boron doping rete moisture absorption loss of stability and destruction aluminum membranous layer, and the method in the of the present invention and existing document is compared and is had processing step characteristics few, simple to operate.
In the method for the invention; Do not relate to the use of boron oxide compound or other kind boron compound; But aluminium boron simple substance atom coexists as in the aluminium boron film layer; This aluminium boron film layer has the technological merit of good in integrity, stability height, strong adhesion by the preparation of technical methods such as magnetron sputtering method, electron-beam vapor deposition method or silk screen print method.
Description of drawings
Crystalline silicon (not comprising passivating film) the laser auxiliary aluminum boron codope method diagrammatic sketch that Fig. 1 proposes for the present invention:
1 crystal silicon chip, 2 aluminium boron film layers, 3 laser beams.
Crystalline silicon (comprising passivating film) the laser auxiliary aluminum boron codope method diagrammatic sketch that Fig. 2 proposes for the present invention:
1 crystal silicon chip, 2 passivating films, 3 aluminium boron film layers, 4 laser beams.
Embodiment
Facing crystalline silicon laser auxiliary aluminum boron codope of the present invention and electrode preparation method down specifically describes.
(1) select impurity concentration to be lower than 1 x 10
15Atoms/cm
3, thickness is that monocrystalline silicon (100) polished silicon wafer of 300 μ m is a substrate, behind cleaning, drying, adopts magnetron sputtering method to deposit the aluminium boron film layer of 2 μ m thickness in its surface, wherein the content of boron is 0.6wt%.Magnetron sputtering adopts aluminium boron target, and this target is evenly to mix high-pressure molding afterwards through metallic aluminium powder with the pure boron powder of certain content, and sintering forms in a vacuum or under the inert gas shielding atmosphere then.
(2) adopt Nd:YAG near infrared pulsed laser device, optical maser wavelength is 1064nm, and pulse frequency is 4kHz; Burst length is 100ns, and laser power is 1.2W, and lasing beam diameter is 120 μ m; Laser is done the single-point irradiation on aluminium boron film layer, the umber of pulse of shining at this point is set at 6 pulses.Under the irradiation of pulse laser, the aluminium boron film layer region that is shone melts rapidly, simultaneously should the zone the also partial melting of silicon of bottom, form the melting range of the 4.5 μ m degree of depth, this melting range is actually aluminium, boron, silicon three's eutectic.
(3) after laser has been accomplished the pulse irradiation of setting at this point of irradiation; Break off or remove laser, this eutectic after laser radiation stops, cooling rapidly; Silicon is separated out from this eutectic and crystalline growth fast; Part aluminium and boron atom remain in this crystalline silicon and to form the aluminium boron codope, and remaining aluminium and boron will be in this regional surface solidification film forming, and are not excited light-struck aluminium boron film layer with other and are in contact with one another the formation electrode.
So promptly accomplished the preparation of laser auxiliary aluminum boron codope and electrode in the crystalline silicon.Ion microprobe shows that in the detection in this aluminium boron codope zone the doping content of aluminium reaches 3.1 x 10
18Atoms/cm
3, and the doping content of boron reaches 3.6 x 10
19Atoms/cm
3, can see, in the crystalline silicon doping content of boron than aluminium high an one magnitude.
(1) select impurity concentration to be lower than 1 x 10
15Atoms/cm
3, thickness is that monocrystalline silicon (100) polished silicon wafer of 300 μ m is a substrate; Behind cleaning, drying; Using plasma strengthens SiNx, SiOx, SiCx or other compound rete of chemical vapour deposition technique (PECVD) deposition one deck 80nm thickness; This rete has good passivation effect to the surface of crystalline silicon, thereby improves the electrical property of crystalline silicon.This rete is called passivating film.
(2) in (1) step, deposit the aluminium boron film layer of 2 μ m thickness on the prepared passivating film surface in its surface with magnetron sputtering method, wherein the content of boron is 0.8wt%.The target that magnetron sputtering adopted also is an aluminium boron target.
(3) adopt Nd:YAG near infrared pulsed laser device, optical maser wavelength is 1064nm, and pulse frequency is 3.6kHz; Burst length is 100ns, and laser power is 1.1W, and lasing beam diameter is 120 μ m; Laser is done the single-point irradiation on aluminium boron film layer, the umber of pulse of shining at this point is set at 8 pulses.Under the irradiation of pulse laser, the aluminium boron film layer region that is shone melts rapidly, simultaneously should the zone the also partial melting of silicon of bottom, form the melting range of the 5 μ m degree of depth, this melting range is actually aluminium, boron, silicon three's eutectic.
(4) after laser has been accomplished the pulse irradiation of setting at this point of irradiation; Break off or remove laser, this eutectic after laser radiation stops, cooling rapidly; Silicon is separated out from this eutectic and crystalline growth fast; Part aluminium and boron atom remain in this crystalline silicon and to form the aluminium boron codope, and remaining aluminium and boron will be in this regional surface solidification film forming, and are not excited light-struck aluminium boron film layer with other and are in contact with one another the formation electrode.
So promptly accomplished the preparation of laser auxiliary aluminum boron codope and electrode in the crystalline silicon.Ion microprobe shows that in the detection in this aluminium boron codope zone the doping content of aluminium reaches 3.2 x 10
18Atoms/cm
3, and the doping content of boron reaches 4.1 x 10
19Atoms/cm
3, can see, in the crystalline silicon doping content of boron than aluminium high an one magnitude.
(1) selects a slice p type monocrystalline silicon (100); Its resistivity is 2.5 Ω cm; Thickness is 250 μ m, and behind cleaning, drying, using plasma strengthens chemical vapour deposition technique at this silicon chip surface deposition SiOx and SiNx dual layer passivation film; Wherein the thickness of SiOx rete is 20nm, and the thickness of SiNx rete is 60nm.
(2) adopt silk screen print method on the surface of the SiOx/SiNx dual layer passivation film that (1) step is deposited, to print the aluminium boron slurry that one deck does not contain glass dust, its thickness is about 25 μ m, and the mass ratio of boron and aluminium is 1wt% in this aluminium boron slurry.
(3) down the above-mentioned monocrystalline silicon silicon chip that has silk screen printing aluminium boron pulp layer is dried at 200 ℃, drying time is 15 minutes.
(4) with the monocrystalline silicon piece of drying in (3) step heat treatment 8 minutes under 780 ℃ air ambient, be cooled to room temperature then.Organic substance in the aluminium boron pulp layer is with oxidized decomposition, and aluminium boron pulp layer becomes aluminium boron film layer, and wherein boron content is pointed out in the elaboration of above-mentioned (2) step.In addition, pointed in the elaboration like above-mentioned (2) step, the employed aluminium boron of present embodiment slurry does not contain glass dust, and therefore the SiOx/SiNx dual layer passivation film of its bottom will can not destroyed by this slurry in heat treatment process.
(5) adopt Nd:YAG near infrared pulsed laser device, optical maser wavelength is 1064nm, and pulse frequency is 4kHz; Burst length is 1000ns, and laser power is 25W, and lasing beam diameter is 120 μ m; Laser is done the single-point irradiation on aluminium boron film layer, the umber of pulse of shining at this point is set at 15 pulses.Under the irradiation of pulse laser, the aluminium boron film layer region that is shone melts rapidly, simultaneously should the zone the also partial melting of silicon of bottom, form the melting range of the 5 μ m degree of depth, this melting range is actually aluminium, boron, silicon three's eutectic.
(6) after laser has been accomplished the pulse irradiation of setting at this point of irradiation; Break off or remove laser, this eutectic after laser radiation stops, cooling rapidly; Silicon is separated out from this eutectic and crystalline growth fast; Part aluminium and boron atom remain in this crystalline silicon and to form the aluminium boron codope, and remaining aluminium and boron will be in this regional surface solidification film forming, and are not excited light-struck aluminium boron film layer with other and are in contact with one another the formation electrode.
So promptly accomplished the preparation of laser auxiliary aluminum boron codope and electrode in the crystalline silicon.Ion microprobe shows that in the detection in this aluminium boron codope zone the doping content of aluminium reaches 2.9 x 10
18Atoms/cm
3, and the doping content of boron reaches 3.5 x 10
19Atoms/cm
3, can see, in the crystalline silicon doping content of boron than aluminium high an one magnitude.
(1) select a slice p type monocrystalline silicon (100), its resistivity is 2.5 Ω cm, and thickness is 300 μ m, behind cleaning, drying, adopts electron beam evaporation technique to deposit the aluminium boron film layer of 2 μ m thickness in its surface, and wherein the content of boron is 0.7wt%.
(2) adopt Nd:YAG near infrared pulsed laser device, optical maser wavelength is 1064nm, and pulse frequency is 4kHz; Burst length is 100ns, and laser power is 1.3W, and lasing beam diameter is 120 μ m; Laser is done the single-point irradiation on aluminium boron film layer, the umber of pulse of shining at this point is set at 6 pulses.Under the irradiation of pulse laser, the aluminium boron film layer region that is shone melts rapidly, simultaneously should the zone the also partial melting of silicon of bottom, form the melting range of the 4.8 μ m degree of depth, this melting range is actually aluminium, boron, silicon three's eutectic.
(3) after laser has been accomplished the pulse irradiation of setting at this point of irradiation; Break off or remove laser, this eutectic after laser radiation stops, cooling rapidly; Silicon is separated out from this eutectic and crystalline growth fast; Part aluminium and boron atom remain in this crystalline silicon and to form the aluminium boron codope, and remaining aluminium and boron will be in this regional surface solidification film forming, and are not excited light-struck aluminium boron film layer with other and are in contact with one another the formation electrode.
So promptly accomplished the preparation of laser auxiliary aluminum boron codope and electrode in the crystalline silicon.Ion microprobe shows that in the detection in this aluminium boron codope zone the doping content of aluminium reaches 3.1 x 10
18Atoms/cm
3, and the doping content of boron reaches 3.7 x 10
19Atoms/cm
3, can see, in the crystalline silicon doping content of boron than aluminium high an one magnitude.
Claims (4)
1. crystalline silicon laser auxiliary aluminum boron codope and electrode preparation method; It is characterized in that: prepare aluminium boron film layer at surface of crystalline silicon; This aluminium boron film layer provides adulterated al source and boron source, and aluminium boron film layer is by laser radiation, and the zone of being shone is melted and forms aluminium, boron, silicon eutectic; After laser is cut off power supply or removes; This eutectic is cooled off rapidly; Silicon is separated out the beginning crystalline growth immediately, and part aluminium atom and boron atom are stayed in this silicon metal, realizes the aluminium boron codope of crystalline silicon; Remaining aluminium and boron will be in this regional surface solidification film forming, and are not excited light-struck aluminium boron film layer with other and form electrode jointly.
2. a kind of crystalline silicon laser auxiliary aluminum boron codope according to claim 1 and electrode preparation method, it is characterized in that: boron content is 0.001wt%-5wt% in the aluminium boron film layer.
3. a kind of crystalline silicon laser auxiliary aluminum boron codope according to claim 1 and electrode preparation method is characterized in that: aluminium boron film layer adopts magnetron sputtering method, electron-beam vapor deposition method or the preparation of silk screen print method technical method.
4. a kind of crystalline silicon laser auxiliary aluminum boron codope according to claim 1 and electrode preparation method, it is characterized in that: surface of crystalline silicon deposits passivating film in advance, and then at this passivating film surface preparation aluminium boron film layer.
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| CN113109415A (en) * | 2021-03-26 | 2021-07-13 | 南昌大学 | Multilayer film interface position characterization method suitable for secondary ion mass spectrometry |
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Application publication date: 20121226 |