LASER DOPING OF SEMICONDUCTORS

Abstract

The present invention relates to a process for the production of structured, highly efficient solar cells and of photovoltaic elements which have regions of different doping. The invention likewise relates to the solar cells having increased efficiency produced in this way.

Claims

1. Process for the direct doping of a silicon substrate, characterised in that a) a low-viscosity doping ink which is suitable as sol-gel for the formation of oxide layers and comprises at least one doping element selected from the group boron, gallium, silicon, germanium, zinc, tin, phosphorus, titanium, zirconium, yttrium, nickel, cobalt, iron, cerium, niobium, arsenic and lead is printed onto the substrate surface, over the entire surface or selectively, and dried, b) this step is optionally repeated with a low-viscosity ink of the same or different composition, c) doping by diffusion is optionally carried out by temperature treatment at temperatures in the range from 750 to 1100° C., d) doping of the substrate is carried out by laser irradiation, and e) repair of the damage induced in the substrate by the laser irradiation is optionally carried out by a tubular furnace step or in-line diffusion step at elevated temperature, and f) when the doping is complete, the glass layer formed from the applied ink is removed again, where steps b) to e) can, depending on the desired doping result, be carried out in a different sequence and optionally repeated.

2. Process according to claim 1, characterised in that a temperature treatment is carried out at temperatures in the range from 750 to 1100° C. for the doping by diffusion after laser irradiation for doping of the substrate, where repair of the damage induced in the substrate by the laser irradiation is carried out at the same time.

3. Process according to claim 1, characterised in that a low-viscosity doping ink which is suitable as sol-gel for the formation of oxide layers and comprises at least one doping element selected from the group boron, phosphorus, antimony, arsenic and gallium is printed on.

4. Process according to claim 1, characterised in that the low-viscosity ink is printed on by a printing process selected from the group spin coating, dip coating, drop casting, curtain coating, slot-die coating, screen printing, flexographic printing, gravure printing, ink-jet printing, aerosol jet printing, offset printing, microcontact printing, electrohydrodynamic dispensing, roller coating, spray coating, ultrasonic spray coating, pipe jetting, laser transfer printing, pad printing, flat-bed screen printing and rotation screen printing.

5. Process according to claim 1, characterised in that the low-viscosity ink is printed on by ink-jet printing.

6. Process according to claim 1, characterised in that doping is carried out directly from the printed and dried-on glass after boron diffusion with exclusion of an oxidation process of the “boron skin”.

7. Process according to claim 1, characterised in that structured, highly efficient solar cells which have regions of different doping are produced by at least one two-stage doping with only one thermal diffusion or high-temperature treatment of the substrate.

8. Process according to claim 1, characterised in that a glass layer which comprises at least one doping element selected from the group boron, gallium, silicon, germanium, zinc, tin, phosphorus, titanium, zirconium, yttrium, nickel, cobalt, iron, cerium, niobium, arsenic and lead is generated on the substrate surface over the entire surface or selectively in step a) by gas-phase deposition by means of PECVD (plasma-enhanced chemical vapour deposition), APCVD (atmospheric pressure chemical vapour deposition), ALD (atomic layer deposition) or sputtering.

9. Process according to claim 1, characterised in that the glass layer is removed by means of hydrofluoric acid when the doping is complete.

10. Solar cells, produced by a process according to claim 1.

11. Photovoltaic elements, produced by a process according to claim 1.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0065] In principle, the increase in charge-carrier generation improves the short-circuit current of the solar cell. Although the possibility of improving the performance compared with conventional solar cells owing to many technological advances still appears to exist to the person skilled in the art, it is, however, no longer extraordinary, since the silicon substrate, even as indirect semiconductor, is capable of absorbing the predominant proportion of the incident solar radiation. A significant increase in the current yield is only still possible using, for example, solar-cell concepts which concentrate the solar radiation. A further parameter which characterises the performance of the solar cell is the so-called open terminal voltage or simply the maximum voltage that the cell is able to deliver. The level of this voltage is dependent on several factors, inter alia the maximum achievable short-circuit current density, but also the so-called effective charge-carrier lifetime, which is itself a function of the material quality of the silicon, but also a function of the electronic passivation of the surfaces of the semiconductor. In particular, the two last-mentioned properties and parameters play an essential role in the design of highly efficient solar-cell architectures and were originally amongst the main factors responsible for the possibility of increasing the performance in novel types of solar cell. Some novel types of solar cell were already mentioned in the introduction. Going back to the concept of the so-called selective or two-stage emitter (cf. FIG. 1), the principle can be outlined diagrammatically as follows with reference to its mechanism hiding behind the increase in efficiency, with reference to FIG. 1:

[0066] FIG. 1: Diagrammatic and simplified representation (not to scale) of the front of a conventional solar cell (back ignored). The figure shows the two-stage emitter, which arises from two doped regions, in the form of different sheet resistances. The different sheet resistances are attributable to different profile depths of the two doping profiles, and are thus generally also associated with different doses of dopants. The metal contacts of the solar cells to be manufactured from such structural elements are always in contact with the more strongly doped regions.

[0067] The front of the solar cell, at least generally, is provided with the so-called emitter doping. This can be either n-type or p-type, depending on the base material used (the base is then doped in the opposite manner). The emitter, in contact with the base, forms the pn junction, which is able to collect and separate the charge carriers forming in the solar cell via an electric field present over the junction. The minority charge carriers here are driven from the base into the emitter, where they then belong to the majorities. These majorities are transported further in the emitter zone and can be transported out of the cell as current via the electrical contacts located on the emitter zone. A corresponding situation applies to the minorities, which are generated in the emitter and can be transported away via the base. In contrast to the minorities in the base, these have a very short effective carrier lifetime of in the region of up to only a few nanoseconds in the emitter. This arises from the fact that the recombination rate of the minorities is in simplified terms inversely proportional to the doping concentration of the respective region in the silicon; i.e. the carrier lifetime of the respective minorities in the emitter region of a solar cell, which itself represents a highly doped zone in the silicon, can be very short, i.e. very much shorter than in the base, which is doped to a relatively low extent. For this reason, the emitter regions of the silicon wafer are, if possible, made relatively thin, i.e. have little depth in relation to the thickness of the substrate as a whole, in order that the minorities generated in this region, which then have a very short lifetime, which is inherent in the system, have sufficient opportunity, or indeed time, to achieve the pn junction and to be collected and separated at the latter and then driven into the base as majorities. The majorities generally have a carrier lifetime which should be regarded as infinite. If it is desired to make this process more efficient, the emitter doping and depth then inevitably have to be reduced in order that more minorities having a longer carrier lifetime can be generated and driven into the base as majorities transporting the current. Conversely, the emitter screens the minorities from the surface. The surfaces of a semiconductor are always very recombination-active. This recombination activity can be reduced very greatly (by up to seven orders of magnitude, measured from the effective surface recombination rate compared with a surface which has, for example, not been passivated) by the creation and deposition of electronic passivation layers.

[0068] The creation of an emitter having a sufficiently steep doping profile supports passivation of the surface in one aspect:

[0069] The carrier lifetime of the minorities in these regions becomes so short that their average lifetime only allows an extremely low quasi-static concentration. Since the recombination of charge carriers is based on the bringing together of minorities and majorities, simply too few minorities which are able to recombine with majorities directly at the surface are present in this case.

[0070] Significantly better electronic passivation than that of an emitter is achieved by means of dielectric passivation layers. On the other hand, however, the emitter is still partially responsible for the creation of the electrical contacts to the solar cell, which must be ohmic contacts. They are obtained by driving the contact material, generally silver, into the silicon crystal, where the so-called silicon-silver contact resistance is dependent on the level of doping of the silicon at the surface to be contacted. The higher the doping of the silicon, the lower the contact resistance can be. The metal contacts on the silicon are likewise very strongly recombination-active, for which reason the silicon zone below the metal contacts should have very strong and very deep emitter doping. This doping screens the minorities from the metal contacts, and at the same time a low contact resistance and thus very good ohmic conductivity are achieved. By contrast, in all locations where the incident sunlight falls directly on the solar cell, the emitter doping should be very low and relatively flat (i.e. not very deep) in order that sufficient minorities having a sufficient lifetime can be generated by the incident solar radiation and driven into the base as majorities via separation at the pn junction.

[0071] Surprisingly, experiments have now shown that a solar cell which has two different emitter dopings, more precisely one region having shallow doping and one region having very deep and very high doping, which lie directly below the metal contacts has significantly higher efficiencies. This concept is referred to as a selective or two-stage emitter. The corresponding concept is based on so-called selective back surface fields. Consequently, two differently doped regions must be achieved in dopings structured at the surface of the solar cell.

[0072] The experiments have shown that the present object can be achieved, in particular, by achieving these structured dopings. The doping processes described in the introduction are generally based on shallow deposition and likewise shallow drive-in of the deposited dopant. Selective triggering in order to achieve different doping strengths is generally not provided and also cannot readily be achieved in the absence of further structuring and mask processes.

[0073] Accordingly, the present process consists in a simplified production process compared with the two-stage or selective emitter structures described above.

[0074] More generally, the process describes a simplification of the production of zones doped with different strengths and depths (n and p) starting from the surface of a silicon substrate, where the term “strength” can, but does not necessarily have to, describe the level of the achievable surface concentration. This may be the same in both cases in the case of zones doped in two stages. The different strength of the doping then arises via the different penetration depth of the dopant and the associated different integral doses of the respective dopant. The present process thus at the same time claims the inexpensive and simplified production of solar cell structures having at least one structural motif which has two-stage doping. These may be repeated briefly below: [0075] PERC solar cells [0076] PERT solar cells [0077] PERL solar cells [0078] MWT solar cells [0079] MWT-PERC, MWT-PERT and MWT-PERL solar cells derived therefrom [0080] bifacial solar cells having a homogeneous and selective back surface field [0081] back surface contact cells [0082] back surface contact cells with interdigital contacts.

[0083] The simplified production process is in the present case based on doping media which can be printed simply and inexpensively. The doping media correspond at least to those disclosed in the patent applications WO 2012/119685 A1 and WO 2014/101990 A1, but may have different compositions and formulations. The doping media have a viscosity of preferably less than 500 mPa*s, but typically in a range from greater than 1 to 50 mPa*s, measured at a shear rate of 25 1/s and a temperature of 23° C., and are thus, owing to their viscosity and their other formulation properties, extremely well adapted to the individual requirements of screen printing. They are pseudo-plastic and may furthermore also have thixotropic behaviour. The printable doping media are applied to the entire surface to be doped with the aid of a conventional screen-printing machine. Typical, but non-restrictive print settings are mentioned in the course of the present description. The printed doping media are subsequently dried on in a temperature range between 50° C. and 750° C., preferably between 50° C. and 500° C., particularly preferably between 50° C. and 400° C., using one or more heating steps to be carried out sequentially (heating by means of a step function) and/or a heating ramp and compacted for vitrification, resulting in the formation of a handling- and abrasion-resistant layer having a thickness of up to 500 nm. The further processing in order to achieve two-stage dopings of the substrates treated in this way may subsequently comprise two possible process sequences, which will be outlined briefly below.

[0084] The process sequence will be described exclusively for the possible doping of the silicon substrate with boron as dopant. Analogous descriptions, albeit deviating slightly in the necessity of carrying them out, can also be applied to phosphorus as dopant. [0085] 1. Heat treatment of the layers printed onto the surfaces, compacted and vitrified is carried out at a temperature in the range between 750° C. and 1100° C., preferably between 850° C. and 1100° C., particularly preferably between 850° C. and 1000° C. As a consequence, atoms having a doping action on silicon, such as boron, are released to the substrate by silicothermal reduction of their oxides (so long as the dopants are present in the form of free and/or bound oxides in the matrix of the dopant source) on the substrate surface, whereby the conductivity of the silicon substrate is specifically advantageously influenced as a consequence of the doping commencing. It is particularly advantageous here that, owing to the heat treatment of the printed substrate, the dopants are transported to depths of up to 1 μm, depending on the treatment duration, and electrical sheet resistances of less than 10 Ω/□ are achieved. The surface concentration of the dopant can adopt values greater than or equal to 1*10.sup.19 to greater than 1*10.sup.21 atoms/cm.sup.3 here and is dependent on the type of dopant used in the printable oxide medium. In the case of doping with boron, a thin so-called boron skin, which is generally regarded as a phase consisting of silicon boride which forms as soon as the solubility limit of boron in silicon is exceeded (this is typically 3-4*10.sup.20 atoms/cm.sup.3), forms on the silicon surface. The formation of this boron skin is dependent on the diffusion conditions used, but cannot be prevented within the bounds of classical gas-phase diffusion and doping. However, it has been found that the choice of the formulation of the printable doping media enables a considerable influence to be exerted on the formation and the formed thickness of the boron skin. The boron skin present on the silicon substrate can be used by means of suitable laser irradiation as dopant source for the locally selective further drive-in of the dopant boron which deepens the doping profile. To this end, however, the wafers treated in this way must be removed from the diffusion and doping furnace and treated by means of laser irradiation. At least the silicon wafer surface regions remaining and not exposed to the laser irradiation subsequently still have an intact boron skin. Since the boron skin has in numerous investigations proven to be counterproductive for the electronic surface passivation ability of the silicon surfaces, it appears essential to eliminate it in order to prevent disadvantageous diffusion and doping processes. [0086] The successful elimination of this phase can be achieved by means of various oxidative processes, such as, for example, low-temperature oxidation (typically at temperatures between 600° C. and 850° C.), a brief oxidation step below the diffusion and doping temperature in which the gas atmosphere is adjusted in a specific and controlled manner by enrichment of oxygen, or by the constant drive-in of a small amount of oxygen during the diffusion and doping process. [0087] The choice of oxidation conditions influences the doping profile obtained: in the case of low-temperature oxidation, exclusively the boron skin is oxidised at a sufficiently low temperature, and only slight surface depletion of the dopant boron, which in principle dissolves better in the silicon dioxide formed during the oxidation, takes place, while not only exclusively the boron skin, but also parts of the doped silicon actually desired, which, owing to the high doping, has a significantly increased oxidation rate (increase in the rate by a factor of up to 200) is also oxidised and consumed in the remaining two oxidation steps. Significant depletion of the dopant can take place at the surface, which requires thermal after-treatment, a distribution or drive-in step of the dopant atoms which have already diffused into the silicon. However, in this case the dopant source presumably supplies only little or no further dopant to the silicon. The oxidation of the silicon surface and of the boron skin present thereon can also be carried out and significantly accelerated by the additional introduction of steam and/or chlorine-containing vapours and gases. An alternative method for elimination of the boron skin consists in wet-chemical oxidation by means of concentrated nitric acid and subsequent etching of the silicon dioxide layer obtained on the surface. This treatment must be carried out in a plurality of cascades for complete elimination of the boron skin, where this cascade is not accompanied by significant surface depletion of the dopant. [0088] The sequence outlined here for the production of regions with locally selective or two-stage doping is distinguished by the following at least ten steps: [0089] Printing of the dopant source.fwdarw. [0090] Compaction.fwdarw. [0091] Introduction into doping furnace.fwdarw. [0092] Thermal diffusion and doping of the substrate.fwdarw. [0093] Removal of the samples.fwdarw. [0094] Laser irradiation for selective doping from the boron skin.fwdarw. [0095] Introduction of the samples into the furnace.fwdarw. [0096] Oxidative removal of the boron skin.fwdarw. [0097] Further drive-in treatment.fwdarw. [0098] Removal from the furnace. [0099] 2. The drying and compaction of the dopant applied over the entire surface is followed by local irradiation of the substrate by means of laser radiation. To this end, the layer present on the surface does not necessarily have to be completely compacted and vitrified. Through a suitable choice of the parameters characterising the laser radiation treatment, such as pulse length, illuminated area in the radiation focus, repetition rate on use of pulsed laser radiation, the printed-on and dried-on layer of the dopant source can release the dopants having a doping action which are present therein to the surrounding silicon, which is preferably located below the printed-on layer. Through the choice of the laser energy coupled onto the surface of the printed substrate, the sheet resistance of the substrate can be specifically influenced and controlled. Higher laser energies here give rise to lower sheet resistance, which, in simplified terms, corresponds to a higher dose of the introduced dopant and a greater depth of the doping profile. If necessary, the printed-on layer of the dopant source can subsequently be removed from the surface of the wafer without a residue with the aid of aqueous solutions containing both hydrofluoric acid and also hydrofluoric acid and phosphoric acid or by means of corresponding solutions based on organic solvents, and also through the use of mixtures of the two above-mentioned etching solutions. The removal of the dopant source can be accelerated and promoted by the action of ultrasound during the use of the etching mixture. Alternatively, the printed-on dopant source can be left on the surface of the silicon wafer. The wafer coated in this way can be doped on the entire coated silicon wafer surface by thermally induced diffusion in a conventional doping furnace. This doping can be carried out in doping furnaces usually used. These can be either tubular furnaces (horizontal and/or vertical) or horizontally working through-flow furnaces, in which the gas atmosphere used can be set specifically. As a consequence of the thermally induced diffusion of the dopants from the printed-on dopant source into the underlying silicon of the wafer, doping of the entire wafer is achieved in combination with a change in the sheet resistance. The degree of doping is dependent on the respective process parameters used, such as, for example, process temperature, plateau time, gas flow rate, the type of heating source used and the temperature ramps for setting the respective process temperature. In a process of this type, depending on the regions treated by means of laser beam doping and using a doping ink formulation according to the invention, sheet resistances of about 75 ohm/sqr are usually achieved at a diffusion time of 30 minutes at 950° C. and with a gas flow rate of five standard litres of N.sub.2 per minute. In the case of the treatment mentioned above, the wafers can optionally be pre-dried at temperatures of up to 500° C. The diffusion is followed directly, as already described in greater detail above under paragraph 1., by oxidative removal of the so-called boron skin, but also optionally redistribution of the boron dissolved in the silicon for adaptation and manipulation of the doping profile which can be established. The above-mentioned sheet resistance can be obtained reproducibly, based on the procedure just outlined. Further details on the performance and corresponding further process parameters are described in greater detail in the following examples. [0100] The regions already defined previously by means of laser beam treatment and the dopants dissolved in these regions are likewise stimulated to further diffusion as a consequence of the thermally induced diffusion of the dopants. Owing to this additional diffusion, the dopants are able to penetrate deeper into the silicon at these points and accordingly shape a deeper doping profile. At the same time, dopant can subsequently be supplied to the silicon from the dopant source located on the wafer surface. Doped zones which have a significantly deeper doping profile and also a significantly higher dose of the dopant boron than those regions which were subjected to thermally induced diffusion exclusively in a doping furnace thus form in the regions which were previously subjected to the laser radiation treatment. In other words, two-stage dopings, also known as selective dopings, arise. The latter can be used, for example, in the production of solar cells having a selective emitter, in the production of bifacial solar cells (having a selective emitter/uniform (one-stage) BSF, having a uniform emitter/selective BSF and having a selective emitter/selective BSF), in the production of PERT cells, or also in the production of IBC solar cells. [0101] The comparable principle also applies to the thermally induced post-diffusion of silicon wafers which have been pretreated by means of laser radiation, which were previously freed from the presence of the printed-on dopant source by means of etching. In this case, the dopant boron is driven deeper into the silicon. Owing to the removal of the printed-on dopant source which took place before this process, however, dopant can no longer subsequently be supplied to the silicon. The dose dissolved in the silicon will remain constant, while the average concentration of the dopant in the doped zone is reduced owing to increasing profile depth and associated reduction in the direct surface concentration of the dopant. This procedure can be used for the production of IBC solar cells. Strips of one polarity are generated from the dried-on doping ink by means of laser beam doping alongside strips having the opposite polarity, which can in turn be obtained with the aid of laser beam doping from a printed-on and dried-on phosphorus-containing doping ink. The sequence thus outlined for the production of regions with locally selective or two-stage doping is distinguished by the following at least eight steps: [0102] Printing of the dopant source.fwdarw. [0103] Drying.fwdarw. [0104] Laser irradiation from the dopant source.fwdarw. [0105] Introduction into the doping furnace.fwdarw. [0106] Thermal diffusion and (further) doping of the substrate.fwdarw. [0107] Oxidative removal of the boron skin.fwdarw. [0108] Further drive-in treatment.fwdarw. [0109] Removal of the samples from the furnace (cf. FIG. 3).

[0110] The two process cascades described above represent possibilities for the production of two-stage, or so-called selective, dopings. On the basis of the above-mentioned embodiments and the associated number of process steps to be carried out, the second embodiment described represents the alternative which is more attractive and to be preferred owing to the smaller number of process steps.

[0111] In both embodiments, the doping action of the printed-on dopant source can be influenced by the choice of the respective process parameters, in particular those of the laser beam treatment or laser beam doping. However, the doping action can also be crucially influenced and controlled by the composition of the printable dopant source (cf. FIG. 2). If desired, two-stage dopings can take place not exclusively only through the use of a printable dopant source followed by a further dopant source, but instead they can also be generated through the use of two printable dopant sources. The dose of dopants which is to be introduced into the silicon to be doped can, in particular, be specifically influenced and controlled by the above-mentioned embodiment via the dopant concentrations present in the dopant sources used.

[0112] FIG. 2 shows a diagrammatic and simplified representation (not to scale) of the doping process according to the invention induced by laser radiation treatment (cf. FIG. 3) of printable doping inks on silicon wafers, where printable doping inks of different compositions (such as, for example, containing different concentrations of the dopant) can be employed.

[0113] As described, both two-stage dopings and also structured dopings and dopings provided with opposite polarities can be produced very easily in a simple and inexpensive manner on silicon wafers by the process according to the invention using the novel printable doping inks still to be characterised below, making in total only one classical high-temperature step (thermally induced diffusion) necessary (cf. FIG. 4).

[0114] The opposite polarities may advantageously both be located on one side of a wafer, or on opposite sides, or finally represent a mixture of the two above-mentioned structural motifs. Furthermore, it is possible for both polarities to have two-stage doping regions, but they do not necessarily have to have both polarities. It is likewise possible to produce structures in which polarity 1 has a two-stage doping, while polarity 2 does not contain a two-stage doping. This means that the process described here can be carried out in a very variable manner. No further limits are set for the structures of the regions provided with opposite dopings, apart from the limits of the respective structure dissolution during the printing process and those which are inherent in the laser beam treatment. The representations of FIGS. 3, 4 and 5 depict various embodiments of the process according to the invention:

[0115] FIG. 3 shows a diagrammatic and simplified representation (not to scale) of the doping process according to the invention induced by laser radiation treatment of printable doping inks on silicon wafers.

[0116] FIG. 4 shows a diagrammatic and simplified representation (not to scale) of the doping process according to the invention induced by laser radiation treatment of printable doping inks on silicon wafers taking into account the generation of adjacent dopings of different polarities, which are in each case carried out in two stages (pale=weak doping, dark=stronger doping).

[0117] FIG. 5 shows a diagrammatic and simplified representation (not to scale) of the doping process according to the invention induced by laser radiation treatment of printable doping inks on silicon wafers taking into account the generation of adjacent dopings of different polarities, which are in each case carried out in two stages (light=weak doping, dark=stronger doping). The printed and dried-on dopant sources can be sealed with possible top layers in one of the possible process variants. The top layers can be applied to the printed and dried-on dopant sources, inter alia both after the laser beam treatment and also before it. In the present FIG. 5, the top layer has been supplemented with the printed and dried-on dopant source by thermal diffusion after the laser beam treatment.

[0118] The present invention thus encompasses an alternative inexpensive process which can be carried out simply for the production of solar cells with more effective charge generation, but also the production of alternative, printable dopant sources which can be produced inexpensively, deposition thereof on the silicon substrate, and selective one-stage and also selective two-stage doping thereof.

[0119] The selective doping of the silicon substrate can, but does not necessarily have to, be achieved here by means of a combination of initial laser beam treatment of the printed and dried-on dopant source and subsequent thermal diffusion. The laser beam treatment of silicon wafers may be associated with damage to the substrate itself and thus represents an inherent disadvantage of this process inasmuch as this damage, which in some cases extends deep into the silicon, cannot be at least partially repaired by subsequent treatment. In the present process, the laser beam treatment may be followed by thermal diffusion, which contributes to repair of the radiation-induced damage. Furthermore, the metal contacts (cf. FIG. 1) in this type of production of structures doped in two stages are deposited directly on the regions exposed to the laser radiation. The silicon-metal interface is generally characterised by a very high recombination rate (in the order of 2*10.sup.7 cm/s), meaning that possible damage in the strongly doped zone of the region doped in two stages is not significant for the performance of the component as a consequence of the superordinate limiting of the charge-carrier lifetime on the metal contact.

[0120] Surprisingly, it has thus been found that the use of printable doping media, as described in the patent applications WO 2012/119685 A1 and WO 2014/101990 A1, provides the possibility of directly doping silicon substrates by laser beam treatment of a printed-on and dried-on medium. This doping can be achieved locally and without further activation of the dopants, as is usually achieved by classical thermal diffusion. In a subsequent step, conventional thermal diffusion, the dopant introduced into the silicon can either be driven in deeper or the dopant already dissolved can be driven in deeper and further dopant can subsequently be transferred from the dopant source into the silicon, in the latter case causing an increase in the dose of the dopant dissolved in the silicon. The dopant source printed onto the wafer and dried can have a homogeneous dopant concentration. This dopant source can, for this purpose, be applied to the entire surface of the wafer or printed on selectively. Alternatively, dopant sources of different compositions and different polarities can be printed onto the wafer in any desired sequence. To this end, the sources can, for example, be processed in two successive printing and drying steps. The preferred embodiments of the present invention are reproduced in the following examples.

[0121] As stated above, the present description enables the person skilled in the art to use the invention comprehensively. Even without further comments, it will therefore be assumed that a person skilled in the art will be able to utilise the above description in the broadest scope.

[0122] Should anything be unclear, it goes without saying that the cited publications and patent literature should be consulted. Accordingly, these documents are regarded as part of the disclosure content of the present description. This applies, in particular, to the disclosure content of patent applications WO 2012/119685 A1 or WO 2014/101990 A1, since the compositions described in these applications are particularly suitable for use in the present invention.

[0123] For better understanding and in order to illustrate the invention, examples are given below which are within the scope of protection of the present invention. These examples also serve to illustrate possible variants. Owing to the general validity of the inventive principle described, however, the examples are not suitable for reducing the scope of protection of the present application to these alone.

[0124] Furthermore, it goes without saying to the person skilled in the art that, both in the examples given and also in the remainder of the description, the component amounts present in the compositions always only add up to 100% by weight, mol-% or % by vol., based on the entire composition, and cannot exceed this, even if higher values could arise from the percent ranges indicated. Unless indicated otherwise, % data are therefore regarded as % by weight, mol-% or % by vol.

[0125] The temperatures given in the examples and the description and in the claims are always in ° C.

EXAMPLES

Example 1

[0126] A mirror-etched 6″ CZ wafer having a resistivity of 2 ohm*cm is coated with a boron doping ink in accordance with one of the patent applications WO 2012/119685 A1 or WO 2014/101990 A1 via spin coating, giving a layer thickness of between 50 nm and 200 nm after complete drying thereof at 600° C. The sample is dried for five minutes at 300° C. on a conventional laboratory hotplate and subsequently, after introduction into the doping furnace, subjected to a further drying step at 600° C. for 20 minutes. The sample is then subjected to boron diffusion and heated at a temperature of 930° C. in an inert-gas atmosphere (nitrogen gas) for 30 minutes. In order to drive in the boron doping deeper, individual points of the sample are treated by means of an Nd:YAG nanosecond laser having a wavelength of 532 nm and different laser fluence (pulse power). After the laser treatment, the glass layer is removed by means of dilute hydrofluoric acid, and the resultant doping profiles are characterised by means of electrochemical capacitance-voltage (ECV) measurement and by means of secondary ion mass spectrometry (SIMS). The doped reference sample has a sheet resistance of 52 ohm/sqr, whereas the samples treated with the laser radiation have, according to four-point measurement, a sheet resistance of 28 ohm/sqr, 10 ohm/sqr and 5 ohm/sqr (in the sequence of their appearance in FIG. 6).

[0127] FIG. 6 shows ECV doping profiles before and after the treatment of samples which have already been subject to thermal diffusion and not subsequent oxidation. The doping was carried out by means of a boron ink according to the invention. The abbreviation “OV” noted in the key stands for the laser beam scanning the doped wafer point-by-point and denotes the degree of overlap of the laser radiation diameters nominally positioned alongside one another. The values given a ter the degree of overlap correspond to the energy densities in each case introduced onto the silicon surface. The reference curve corresponds to the doping achieved as a consequence of thermal diffusion even before commencement of the laser radiation treatment.

[0128] FIG. 7 shows SIMS doping profiles before (black) and after the treatment of samples which have already been subject to thermal diffusion without subsequent oxidation (blue). The doping was carried out by means of a boron ink according to the invention. The abbreviation “Ox” noted in the key stands for the laser beam scanning the doped wafer point-by-point and denotes the degree of overlap of the laser radiation diameters nominally positioned alongside one another. The values given after the degree of overlap correspond to the energy densities in each case introduced onto the silicon surface. The reference curve corresponds to the doping achieved as a consequence of thermal diffusion even before commencement of the laser radiation treatment.

[0129] It is evident from the ECV profiles that increased doping of the substrate from the so-called boron skin occurs from a laser fluence of 1.1 J/cm.sup.2. The supplementary SIMS profiles show a reduction in the surface concentration of the boron for the sample subsequently treated with the laser radiation. The boron present in the boron skin is driven further into the silicon wafer. The depth of the doping profile of boron increases from 1 μm to ˜1.5 μm as a consequence of the treatment with the laser radiation.

Example 2

[0130] A mirror-etched 6″ CZ wafer having a resistivity of 2 ohm*cm is coated with a boron doping ink in accordance with one of the patent applications WO 2012/119685 A1 or WO 2014/101990 A1 via spin coating, giving a layer thickness of between 50 nm and 200 nm after complete drying thereof at 600° C. The sample is dried for five minutes at 300° C. on a conventional laboratory hotplate and subsequently, after introduction into the doping furnace, subjected to a further drying step at 600° C. for 20 minutes. The sample is then subjected to boron diffusion and heated at a temperature of 930° C. in an inert-gas atmosphere (nitrogen) for 30 minutes. In order to remove the boron-rich layer, the so-called boron skin, occurring during the boron diffusion, a moist oxidation is carried out in situ at 850° C. for 25 min after the diffusion. In order to drive in the boron doping deeper, individual points of the sample are treated by means of an Nd:YAG nanosecond laser having a wavelength of 532 nm and different laser fluence (pulse power). After the laser treatment, the glass layer is removed by means of dilute hydrofluoric acid, and the doping profiles resulting in the silicon are characterised by means of electrochemical capacitance-voltage (ECV) measurement and by means of secondary ion mass spectrometry (SIMS). The sheet resistance of the reference sample, determined by means of four-point measurement, is 85 ohm/sqr, whereas the sheet resistances of the samples treated with the laser radiation are 85 ohm/sqr and 100 ohm/sqr (in the sequence of their appearance in FIG. 8).

[0131] FIG. 8 shows ECV doping profiles before and after the treatment of samples which have already been subject to thermal diffusion and subsequent oxidation. The doping was carried out by means of a boron ink according to the invention. The abbreviation “OV” noted in the key stands for the laser beam scanning the doped wafer point-by-point and denotes the degree of overlap of the laser radiation diameters nominally positioned alongside one another. The values given after the degree of overlap correspond to the energy densities in each case introduced onto the silicon surface. The reference curve corresponds to the doping achieved as a consequence of thermal diffusion even before commencement of the laser radiation treatment.

[0132] FIG. 9 shows SIMS doping profiles before (black) and after the treatment of samples which have already been subject to thermal diffusion and subsequent oxidation (red & blue) as a function of laser irradiation parameters used. The doping was carried out by means of a boron ink according to the invention. The abbreviation “Ox” noted in the key stands for the laser beam scanning the doped wafer point-by-point and denotes the degree of overlap of the laser radiation diameters nominally positioned alongside one another. The values given after the degree of overlap correspond to the energy densities in each case introduced onto the silicon surface. The reference curve corresponds to the doping achieved as a consequence of thermal diffusion even before commencement of the laser radiation treatment.

[0133] The sheet resistances measured give no indication of a significant change in the dopings compared with the reference sample. No subsequent doping is evident compared with the samples having the boron skin still present on the wafer. The doping profiles determined by means of ECV and SIMS show a slight reduction in the surface concentration of the dopant and also a slight increase in the profile depth with increasing energy density introduced by means of the laser. The average doses of dopant, determined by means of integration from the SIMS profiles, give the following values: 1.2*10.sup.15 atoms/cm.sup.2 for the reference and 0.8*10.sup.14 atoms/cm.sup.2 or 0.9*10.sup.14 atoms/cm.sup.2 for the samples subsequently treated with the aid of the laser beam treatment.

Example 3

[0134] A mirror-etched 6″ CZ wafer having a resistivity of 2 ohm*cm is coated with a boron doping ink in accordance with one of the patent applications WO 2012/119685 A1 or WO 2014/101990 A1 via spin coating, giving a layer thickness of between 50 nm and 200 nm after complete drying thereof at 600° C. The sample is dried for five minutes at 300° C. on a conventional laboratory hotplate. The sample is subsequently treated by means of laser radiation in order to induce the doping, to which end individual points of the sample are irradiated by means of an Nd:YAG nanosecond laser having a wavelength of 532 nm and different laser fluence (pulse power). In order to investigate the pure diffusion due to laser treatment, the sheet resistances are determined by means of four-point measurement, and the doping profiles are checked by means of ECV. After the laser beam treatment, the sample is subjected to thermal boron diffusion, for which purpose the sample is heated at a temperature of 930° C. in an inert-gas atmosphere (nitrogen) for 30 minutes. In order to remove the boron-rich layer, the so-called boron skin, occurring during the boron diffusion, a dry oxidation is carried out in situ at 930° C. for 5 min. after the diffusion. After the thermal diffusion, the glass layer is removed by means of dilute hydrofluoric acid, and the resultant doping profiles are characterised by means of electrochemical capacitance-voltage (ECV) measurement and four-point measurement. The sheet resistances of the doped samples are (in the sequence of their appearance in FIG. 10—the sheet resistance of the base-doped wafer was 160 ohm/sqr):

TABLE-US-00001 TABLE 1 Summary of measured sheet resistances as a function of different process procedures: after laser diffusion and after laser diffusion and subsequent thermal diffusion. Processing Sheet resistance [ohm/sqr] Laser diffusion, field 33 (LD ink, 82 33), 66% overlap of adjacent laser dots, energy density: 2.8 J/cm.sup.2 No laser diffusion & thermal 60 diffusion, field 11 (LD & diff. ink, 11) Laser diffusion & thermal 35 diffusion, field 33 (LD & diff. ink, 33), 66% overlap of adjacent laser dots, energy density: 2.8 J/cm.sup.2 Laser diffusion & thermal 65 diffusion, field 38 (LD & diff. ink, 38), 20% overlap of adjacent laser dots, energy density: 1.53 J/cm.sup.2

[0135] FIG. 10 shows ECV doping profiles as a function of various diffusion conditions: after laser diffusion and after laser diffusion and subsequent thermal diffusion. As a consequence of the laser irradiation of the printed-on and dried-on ink, doping of the silicon wafer has been induced, as can clearly be shown with reference to the doping profile in irradiated field 33 (LD, 33). Subsequent thermal treatment (diffusion) of the samples allows the doping to be increased and the doping profile to be driven deeper into the volume of the silicon wafer.

[0136] It can be established, with reference to further sheet resistance measurements, that silicon wafer doping which does not require further activation by means of thermal diffusion is achieved from the printed and dried-on doping ink layer from a laser fluence of 1.4 J/cm.sup.2. Thermal diffusion after the laser irradiation of the samples causes an increase in the profile depth and a reduction in the sheet resistance. Treatment with a high energy density (>2 J/cm.sup.2) introduced by the laser produces very deep and very strongly doped regions.