WO2013028689A2 - Phosphate esters, phosphate-comprising dopants, and methods for fabricating phosphate-comprising dopants using silicon monomers - Google Patents
Phosphate esters, phosphate-comprising dopants, and methods for fabricating phosphate-comprising dopants using silicon monomers Download PDFInfo
- Publication number
- WO2013028689A2 WO2013028689A2 PCT/US2012/051719 US2012051719W WO2013028689A2 WO 2013028689 A2 WO2013028689 A2 WO 2013028689A2 US 2012051719 W US2012051719 W US 2012051719W WO 2013028689 A2 WO2013028689 A2 WO 2013028689A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- phosphate
- polyol
- silicon
- diol
- transesterifying
- Prior art date
Links
- 239000002019 doping agent Substances 0.000 title claims abstract description 47
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 40
- 239000010703 silicon Substances 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 30
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims description 28
- 239000000178 monomer Substances 0.000 title claims description 22
- 150000003014 phosphoric acid esters Chemical class 0.000 title abstract description 10
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 33
- 239000010452 phosphate Substances 0.000 claims abstract description 28
- -1 phosphate ester Chemical class 0.000 claims abstract description 21
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 15
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 10
- 229920005862 polyol Polymers 0.000 claims description 23
- 150000003077 polyols Chemical class 0.000 claims description 23
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 21
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 20
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 19
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 15
- 150000002148 esters Chemical class 0.000 claims description 11
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical group CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 claims description 10
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical group CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 7
- 229960004063 propylene glycol Drugs 0.000 claims description 7
- 235000013772 propylene glycol Nutrition 0.000 claims description 7
- 150000003376 silicon Chemical class 0.000 claims description 7
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical group CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical group CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical group CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical group CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 claims description 6
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical group CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 5
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 5
- 229940035437 1,3-propanediol Drugs 0.000 claims description 5
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 claims description 5
- PTJWCLYPVFJWMP-UHFFFAOYSA-N 2-[[3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)COCC(CO)(CO)CO PTJWCLYPVFJWMP-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- RNFAKTRFMQEEQE-UHFFFAOYSA-N Tripropylene glycol butyl ether Chemical group CCCCOC(CC)OC(C)COC(O)CC RNFAKTRFMQEEQE-UHFFFAOYSA-N 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 5
- 229940093476 ethylene glycol Drugs 0.000 claims description 5
- 229960005150 glycerol Drugs 0.000 claims description 5
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 claims description 5
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 5
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 claims description 5
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- WMDZKDKPYCNCDZ-UHFFFAOYSA-N 2-(2-butoxypropoxy)propan-1-ol Chemical group CCCCOC(C)COC(C)CO WMDZKDKPYCNCDZ-UHFFFAOYSA-N 0.000 claims description 3
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical group COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 claims description 3
- XYVAYAJYLWYJJN-UHFFFAOYSA-N 2-(2-propoxypropoxy)propan-1-ol Chemical group CCCOC(C)COC(C)CO XYVAYAJYLWYJJN-UHFFFAOYSA-N 0.000 claims description 3
- 150000002009 diols Chemical class 0.000 claims description 3
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 3
- LEEANUDEDHYDTG-UHFFFAOYSA-N 1,2-dimethoxypropane Chemical compound COCC(C)OC LEEANUDEDHYDTG-UHFFFAOYSA-N 0.000 claims description 2
- CUVLMZNMSPJDON-UHFFFAOYSA-N 1-(1-butoxypropan-2-yloxy)propan-2-ol Chemical compound CCCCOCC(C)OCC(C)O CUVLMZNMSPJDON-UHFFFAOYSA-N 0.000 claims description 2
- JONNRYNDZVEZFH-UHFFFAOYSA-N 2-(2-butoxypropoxy)propyl acetate Chemical compound CCCCOC(C)COC(C)COC(C)=O JONNRYNDZVEZFH-UHFFFAOYSA-N 0.000 claims description 2
- PCCUVQJBCDUUMM-UHFFFAOYSA-N 2-[2-[2-(2-butoxypropoxy)propoxy]propoxy]propan-1-ol Chemical compound CCCCOC(C)COC(C)COC(C)COC(C)CO PCCUVQJBCDUUMM-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims 3
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims 1
- 150000003624 transition metals Chemical class 0.000 claims 1
- 239000000463 material Substances 0.000 description 20
- 235000021317 phosphate Nutrition 0.000 description 15
- 239000004065 semiconductor Substances 0.000 description 13
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 10
- 230000008569 process Effects 0.000 description 9
- 239000007788 liquid Substances 0.000 description 6
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 5
- 230000007423 decrease Effects 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 238000007641 inkjet printing Methods 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 238000007650 screen-printing Methods 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 150000004762 orthosilicates Chemical class 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- 230000002411 adverse Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000002508 contact lithography Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Natural products CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229960004592 isopropanol Drugs 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000010943 off-gassing Methods 0.000 description 1
- 239000000546 pharmaceutical excipient Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005903 polyol mixture Polymers 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/091—Esters of phosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
Definitions
- the present invention generally relates to phosphosilicates and methods for fabricating phosphosilicate dopants, and more particularly relates to phosphate esters, phosphate-comprising dopants, and methods for fabricating phosphate-comprising esters and dopants using the transesterification of silicon monomers.
- Doping of semiconductor materials with conductivity-determining type impurities, such as n-type and p-type elements, is used in a variety of applications that require modification of the electrical characteristics of the semiconductor materials.
- Phosphorous is conventionally used to form n-type regions in a semiconductor material.
- Phosphorous-comprising dopants can be deposited to form specific patterns using application processes such as screen printing, spray application, spin coating, rotogravure application, inkjet printing, and the like.
- Screen printing involves the use of a patterned screen or stencil that is disposed over a semiconductor material. A liquid dopant is placed on top of the screen and is mechanically pressed through the screen to deposit on the semiconductor material (e.g. solar wafer). If the screen has a pattern formed by areas that have no openings and areas that do have openings, the material can be deposited in a pattern that corresponds to the pattern of the screen.
- Spin application involves spinning the semiconductor material at a high spin speed such as, for example, up to 1200 revolutions per minute or even higher, while spraying the liquid dopant onto the spinning semiconductor material at a desired fluid pressure.
- Spinning causes the liquid dopant to spread outward substantially evenly across the semiconductor material.
- the liquid dopant also can be sprayed onto a semiconductor material at a desired fluid pressure at a position substantially at the center of the semiconductor material.
- the fluid pressure causes the dopant to spread radially and substantially evenly across the wafer.
- Rotogravure printing involves a roller upon which is engraved a pattern.
- Inkjet printing refers to a non-contact printing process whereby a fluid is projected from a nozzle directly onto a substrate to form a desired pattern.
- Each of the various application processes described above utilizes a dopant formulation with a viscosity and polarity suitable for the given process. For example, screen printing requires relatively high viscosity while inkjet printing requires a viscosity low enough so that the dopant can be dispensed from a nozzle.
- Phosphosilicate dopants are often used in the above-described application processes and are typically made by sol-gel processes using polymers and oligomers.
- these dopants suffer from a number of drawbacks.
- such conventional materials typically do not exhibit relatively high viscosity.
- thickers are required, which must be removed during subsequent processing leading to additional challenges.
- the molecular weight of such dopants is unstable, increasing at room temperature. Accordingly, the dopants typically must be transported, used, and stored under refrigeration and typically have a short shelf-life.
- the dopants can be formed with pockets or regions of high phosphorous concentration or high silicon concentration that can adversely affect the material or electrical characteristics of the post-diffusion electrical devices.
- fabrication of the dopants requires the use of solvents that can be volatile and flammable, thus requiring expensive engineering and safety controls.
- the fabrication process utilizes polymers and oligomers mixed directly in a solvent (or solvent mixture) that is limited by its suitability for the polymerization reaction.
- instability of the sol-gel material and volatility of the solvent could dry and clog the printing apparatus. For example, such drying and clogging can result in poor uniformity and damaged screens.
- it is preferable in high volume manufacture processes to have a "pot life" for a screen printer ink of over eight hours to avoid changing screens between personnel shifts.
- phosphorous esters and phosphorous- comprising dopants that can be formulated using silicon monomers. It is also desirable to provide phosphorous esters and phosphorous-comprising dopants that can be fabricated with variable viscosities with molecular weights that can exhibit stability during use and storage. In addition, it is desirable to provide methods for fabricating phosphate esters and phosphorous-comprising dopants. Furthermore, other desirable features and characteristics of the present invention will become apparent from the subsequent detailed description of the invention and the appended claims, taken in conjunction with the accompanying drawings and this background of the invention.
- FIG.1 illustrates a reaction used to fabricate a phosphate ester in accordance with an exemplary embodiment
- FIG. 2 illustrates a reaction used to fabricate a phosphate ester in accordance with another exemplary embodiment.
- phosphate esters and phosphorous-comprising dopants and methods of fabricating such materials are provided herein.
- the materials contemplated herein are fabricated using silicon monomers to form phosphorous and silicon networks. Because the phosphate esters are formed using silicon monomers as opposed to polymers or oligomers used conventionally, the synthesis of the phosphate esters is simple and the viscosity of the phosphate esters can be controlled and varied.
- the viscosity and polarity can be controlled so that the phosphosilicate as a dopant is suitable for a particular method of printing application, such as screen printing, spin coating, inkjet printing, spray application, roller application, and the like.
- the selection of polyols used in the phosphosilicate formation also can usefully regulate viscosity and polarity.
- the phosphorous also is in a non-volatile form, being polymerized into the Si-ester network, with minimal "outgassing", that is, vaporization or diffusion from the dopant to the atmosphere, but provides for maximum doping efficiency.
- the phosphorous and silicon are dispersed evenly throughout the formulation without pockets of high phosphorous concentration or high silicon concentration.
- the molecular weight is stable at room temperature and, thus, the phosphosilicate can be used, transported, and stored at room temperature.
- the methods contemplated herein are simple, less costly, and do not use low-flashpoint solvents such as ethanol, acetone, or isopropyl alcohol.
- a method of fabricating a phosphate ester includes reacting phosphorous pentoxide (P 2 O 5 ) with a polyol to produce a mixture of monoalkyl phosphates and dialkyl phosphates, each with a terminal hydroxyl group, as illustrated in FIG. 1.
- suitable polyols include, but are not limited to, pentaerythritol, dipentaerythritol, tripentaerythritol, hexane diol, pentane diol, glycerol, ethylene glycol, propylene glycol, 1,3-propane diol, butane diol, and the like, and combinations thereof.
- the mixture of monoalkyl phosphates and the dialkyl phosphates then are transesterified with a silicon monomer to form the phosphosilicate ester.
- the silicon monomer can be of the form: where R 1 is any alkyl, aromatic, or vynilic mono-ol, R 2 is any polyol, and n is from 0 to 3.
- Examples of silicon monomers suitable for use include tetraethylorthosilicate (TEOS), tetramethy orthosilicate (TMOS), and the like.
- TEOS tetraethylorthosilicate
- TMOS tetramethy orthosilicate
- other polyols can be added to increase the viscosity of the final dopant.
- a phosphosilicate ester is fabricated by transesterifying an orthosilicate, such as, for example, tetraethylorthosilicate (TEOS), with a polyol to produce a polyol-substituted orthosilicate.
- the silicate can be mono-, di-, tri-, or tetra-substituted with a polyol or polyol mixture and the remaining valences can be occupied with any alkoxy or alkyl group. Any of the above-listed polyols can be used.
- the polyol-substituted orthosilicate then is transesterified with P2O5 to produce a diester linkage.
- the polyol-substituted orthosilicate and P2O5 are combined using any suitable mixing or stirring process that forms a homogeneous solution.
- the resulting phosphate ester is a network comprising phosphates linked to silicate(s) of the form:
- R 1 is any diol or polyol or combination thereof
- R 2 is any alkyl, aromatic, alkoxy, polyhydroxy, or phenoxy group
- R 3 is tripropylene glycol butyl ether, heptanol, hexanol, propylene glycol methyl ether (PGME), dipropylene glycol methyl ether, di-propylene glycol propyl ether, di-propylene glycol butyl ether, butanol, pentanol, octanol, decanol, dodecanol or hydroxyl or any combination of the aforementioned
- n is 1, 2, 3, or 4
- x/y is equal to a value between about 1 to about 200.
- the viscosity and the polarity of the phosphate ester can be adjusted by manipulating the mole ratio of silicon to phosphate. As the amount of phosphate decreases in the ester, the amount of Si-O-alkyl group-O-P linkages decrease and the effective molecular weight of the ester formulation decreases. Accordingly the viscosity of the ester decreases.
- the silicon and phosphorous are present in a mole ratio that ranges from about 1 : 1 Si:P to about 200: 1 Si:P.
- a method of forming a phosphate-comprising dopant includes the steps described above for forming a phosphate ester.
- the method of forming a phosphate-comprising dopant comprises adding a solvent to the P2O5, the polyol- substituted silicon monomer, or a mixture thereof. The presence of the solvent allows for the adjustment of the viscosity of the dopant so that the dopant has a desired viscosity suitable for a particular application process.
- Contemplated solvents include propylene glycol methyl ether (PGME), propylene glycol monoether acetate (PGMEA), l-methoxy-2- propanol, propyleneglycol dimethyl ether, dipropyleneglycol butyl ether, dipropyleneglycol butyl ether acetate, tetrapropyleneglycol butyl ether, tripropylene glycol butyl ether, hexanol, heptanol, and combinations thereof.
- PGME propylene glycol methyl ether
- PMEA propylene glycol monoether acetate
- l-methoxy-2- propanol propyleneglycol dimethyl ether
- dipropyleneglycol butyl ether dipropyleneglycol butyl ether acetate
- tetrapropyleneglycol butyl ether tripropylene glycol butyl ether
- the phosphate ester/the phosphate-comprising dopant has a concentration of transition metal cations of less than 50 parts per billion (ppb). Transition metal cations (e.g., Fe, Cr, Ni, and Cu) negatively affect "minority carrier lifetime," which is an important parameter for solar cells in photovoltaic applications.
- Transition metal cations affect carrier lifetime by providing recombination sites where electrons or holes can recombine rather than flowing to collectors of solar cells and contributing to the electricity generated by the cell. Longer carrier lifetime means a more efficient solar cell.
- Such low metal cation concentrations are possible by using purified P2O5 and polyol-substituted silicon monomers to manufacture the phosphate esters/phosphate-comprising dopants.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Silicon Polymers (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
Phosphate esters, phosphate-comprising dopants, and methods for fabricating phosphate-comprising dopants are provided. In an embodiment, a phosphate ester includes phosphate and silicon wherein the phosphate is linked to the silicon by alkyl groups that are bonded via ester bonds with both the phosphate and the silicon.
Description
PHOSPHATE ESTERS, PHOSPHATE-COMPRISING DOPANTS, AND METHODS FOR FABRICATING PHOSPHATE-COMPRISING DOPANTS USING SILICON
MONOMERS
PRIORITY CLAIMS
[0001] This application claims the benefit of U.S. Provisional Application No. 61/527,245, filed August 25, 201 1, incorporated herein in its entirety.
TECHNICAL FIELD
[0002] The present invention generally relates to phosphosilicates and methods for fabricating phosphosilicate dopants, and more particularly relates to phosphate esters, phosphate-comprising dopants, and methods for fabricating phosphate-comprising esters and dopants using the transesterification of silicon monomers.
BACKGROUND
[0003] Doping of semiconductor materials with conductivity-determining type impurities, such as n-type and p-type elements, is used in a variety of applications that require modification of the electrical characteristics of the semiconductor materials. Phosphorous is conventionally used to form n-type regions in a semiconductor material.
[0004] Phosphorous-comprising dopants can be deposited to form specific patterns using application processes such as screen printing, spray application, spin coating, rotogravure application, inkjet printing, and the like. Screen printing involves the use of a patterned screen or stencil that is disposed over a semiconductor material. A liquid dopant is placed on top of the screen and is mechanically pressed through the screen to deposit on the semiconductor material (e.g. solar wafer). If the screen has a pattern formed by areas that have no openings and areas that do have openings, the material can be deposited in a pattern that corresponds to the pattern of the screen. Spin application involves spinning the semiconductor material at a high spin speed such as, for example, up to 1200 revolutions per minute or even higher, while spraying the liquid dopant onto the spinning semiconductor material at a desired fluid pressure. Spinning causes the liquid dopant to spread outward substantially evenly across the semiconductor material. The liquid dopant also can be sprayed onto a semiconductor material at a desired fluid pressure at a position substantially at the center of the semiconductor material. The fluid pressure causes the dopant to spread
radially and substantially evenly across the wafer. Rotogravure printing involves a roller upon which is engraved a pattern. The liquid dopant is applied to the engraved pattern of the roller, which is pressed against a semiconductor material and rolled across the semiconductor material, thereby transferring the liquid dopant to the semiconductor material according to the pattern on the roller. Inkjet printing refers to a non-contact printing process whereby a fluid is projected from a nozzle directly onto a substrate to form a desired pattern. Each of the various application processes described above utilizes a dopant formulation with a viscosity and polarity suitable for the given process. For example, screen printing requires relatively high viscosity while inkjet printing requires a viscosity low enough so that the dopant can be dispensed from a nozzle.
[0005] Phosphosilicate dopants are often used in the above-described application processes and are typically made by sol-gel processes using polymers and oligomers. However, these dopants suffer from a number of drawbacks. For example, when produced using a sol-gel process, such conventional materials typically do not exhibit relatively high viscosity. Because of the low viscosity, "thickeners" are required, which must be removed during subsequent processing leading to additional challenges. Further, the molecular weight of such dopants is unstable, increasing at room temperature. Accordingly, the dopants typically must be transported, used, and stored under refrigeration and typically have a short shelf-life. In addition, the dopants can be formed with pockets or regions of high phosphorous concentration or high silicon concentration that can adversely affect the material or electrical characteristics of the post-diffusion electrical devices. Moreover, fabrication of the dopants requires the use of solvents that can be volatile and flammable, thus requiring expensive engineering and safety controls. And the fabrication process utilizes polymers and oligomers mixed directly in a solvent (or solvent mixture) that is limited by its suitability for the polymerization reaction. Further, instability of the sol-gel material and volatility of the solvent could dry and clog the printing apparatus. For example, such drying and clogging can result in poor uniformity and damaged screens. Typically, it is preferable in high volume manufacture processes to have a "pot life" for a screen printer ink of over eight hours to avoid changing screens between personnel shifts.
[0006] Accordingly, it is desirable to provide phosphorous esters and phosphorous- comprising dopants that can be formulated using silicon monomers. It is also desirable to provide phosphorous esters and phosphorous-comprising dopants that can be fabricated with variable viscosities with molecular weights that can exhibit stability during use and storage.
In addition, it is desirable to provide methods for fabricating phosphate esters and phosphorous-comprising dopants. Furthermore, other desirable features and characteristics of the present invention will become apparent from the subsequent detailed description of the invention and the appended claims, taken in conjunction with the accompanying drawings and this background of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0007] The various embodiments will hereinafter be described in conjunction with the following drawing figures, wherein like numerals denote like elements, and wherein:
[0008] FIG.1 illustrates a reaction used to fabricate a phosphate ester in accordance with an exemplary embodiment; and
[0009] FIG. 2 illustrates a reaction used to fabricate a phosphate ester in accordance with another exemplary embodiment.
DETAILED DESCRIPTION
[0010] The following detailed description is merely exemplary in nature and is not intended to limit the various embodiment or the application and uses thereof. Furthermore, there is no intention to be bound by any theory presented in the preceding background or the following detailed description.
[0011] Various embodiments of phosphate esters and phosphorous-comprising dopants and methods of fabricating such materials are provided herein. The materials contemplated herein are fabricated using silicon monomers to form phosphorous and silicon networks. Because the phosphate esters are formed using silicon monomers as opposed to polymers or oligomers used conventionally, the synthesis of the phosphate esters is simple and the viscosity of the phosphate esters can be controlled and varied. By manipulating the mole ratio of silicon to phosphorous, the viscosity and polarity can be controlled so that the phosphosilicate as a dopant is suitable for a particular method of printing application, such as screen printing, spin coating, inkjet printing, spray application, roller application, and the like. The selection of polyols used in the phosphosilicate formation also can usefully regulate viscosity and polarity. The phosphorous also is in a non-volatile form, being
polymerized into the Si-ester network, with minimal "outgassing", that is, vaporization or diffusion from the dopant to the atmosphere, but provides for maximum doping efficiency. By covalently linking them, the phosphorous and silicon are dispersed evenly throughout the formulation without pockets of high phosphorous concentration or high silicon concentration. In addition, the molecular weight is stable at room temperature and, thus, the phosphosilicate can be used, transported, and stored at room temperature. Further, compared to sol-gel processing, the methods contemplated herein are simple, less costly, and do not use low-flashpoint solvents such as ethanol, acetone, or isopropyl alcohol.
[0012] In accordance with an exemplary embodiment, a method of fabricating a phosphate ester includes reacting phosphorous pentoxide (P2O5) with a polyol to produce a mixture of monoalkyl phosphates and dialkyl phosphates, each with a terminal hydroxyl group, as illustrated in FIG. 1. Examples of suitable polyols include, but are not limited to, pentaerythritol, dipentaerythritol, tripentaerythritol, hexane diol, pentane diol, glycerol, ethylene glycol, propylene glycol, 1,3-propane diol, butane diol, and the like, and combinations thereof. The mixture of monoalkyl phosphates and the dialkyl phosphates then are transesterified with a silicon monomer to form the phosphosilicate ester. The silicon monomer can be of the form:
where R1 is any alkyl, aromatic, or vynilic mono-ol, R2 is any polyol, and n is from 0 to 3. Examples of silicon monomers suitable for use include tetraethylorthosilicate (TEOS), tetramethy orthosilicate (TMOS), and the like. During transesterification, other polyols can be added to increase the viscosity of the final dopant.
[0013] In another embodiment, as illustrated in FIG. 2, a phosphosilicate ester is fabricated by transesterifying an orthosilicate, such as, for example, tetraethylorthosilicate (TEOS), with a polyol to produce a polyol-substituted orthosilicate. The silicate can be mono-, di-, tri-, or tetra-substituted with a polyol or polyol mixture and the remaining valences can be occupied with any alkoxy or alkyl group. Any of the above-listed polyols can be used. The polyol-substituted orthosilicate then is transesterified with P2O5 to produce a diester linkage. The polyol-substituted orthosilicate and P2O5 are combined using any suitable mixing or stirring process that forms a homogeneous solution.
[0014] The resulting phosphate ester is a network comprising phosphates linked to silicate(s) of the form:
[(R3)Phosphate]y
where R1 is any diol or polyol or combination thereof, R2 is any alkyl, aromatic, alkoxy, polyhydroxy, or phenoxy group, R3 is tripropylene glycol butyl ether, heptanol, hexanol, propylene glycol methyl ether (PGME), dipropylene glycol methyl ether, di-propylene glycol propyl ether, di-propylene glycol butyl ether, butanol, pentanol, octanol, decanol, dodecanol or hydroxyl or any combination of the aforementioned, n is 1, 2, 3, or 4, and x/y is equal to a value between about 1 to about 200.
[0015] The viscosity and the polarity of the phosphate ester can be adjusted by manipulating the mole ratio of silicon to phosphate. As the amount of phosphate decreases in the ester, the amount of Si-O-alkyl group-O-P linkages decrease and the effective molecular weight of the ester formulation decreases. Accordingly the viscosity of the ester decreases. In one embodiment, the silicon and phosphorous are present in a mole ratio that ranges from about 1 : 1 Si:P to about 200: 1 Si:P.
[0016] A method of forming a phosphate-comprising dopant includes the steps described above for forming a phosphate ester. In another embodiment, the method of forming a phosphate-comprising dopant comprises adding a solvent to the P2O5, the polyol- substituted silicon monomer, or a mixture thereof. The presence of the solvent allows for the adjustment of the viscosity of the dopant so that the dopant has a desired viscosity suitable for a particular application process. Contemplated solvents include propylene glycol methyl ether (PGME), propylene glycol monoether acetate (PGMEA), l-methoxy-2- propanol, propyleneglycol dimethyl ether, dipropyleneglycol butyl ether, dipropyleneglycol butyl ether acetate, tetrapropyleneglycol butyl ether, tripropylene glycol butyl ether, hexanol, heptanol, and combinations thereof.
[0017] In addition, in an embodiment, functional additives such as surfactants, crosslinking catalysts, dyes, drying agents, and the like are added to the dopant to aid printing, alignment, film formation, or to control spreading. Excipient materials that are intended only to increase volume can also be used.
[0018] In another embodiment, the phosphate ester/the phosphate-comprising dopant has a concentration of transition metal cations of less than 50 parts per billion (ppb). Transition metal cations (e.g., Fe, Cr, Ni, and Cu) negatively affect "minority carrier lifetime," which is an important parameter for solar cells in photovoltaic applications. Transition metal cations affect carrier lifetime by providing recombination sites where electrons or holes can recombine rather than flowing to collectors of solar cells and contributing to the electricity generated by the cell. Longer carrier lifetime means a more efficient solar cell. Such low metal cation concentrations are possible by using purified P2O5 and polyol-substituted silicon monomers to manufacture the phosphate esters/phosphate-comprising dopants.
[0019] While at least one exemplary embodiment has been presented in the foregoing detailed description of the invention, it should be appreciated that a vast number of variations exist. It should also be appreciated that the exemplary embodiment or exemplary embodiments are only examples, and are not intended to limit the scope, applicability, or configuration of the invention in any way. Rather, the foregoing detailed description will provide those skilled in the art with a convenient road map for implementing an exemplary embodiment of the invention. It being understood that various changes may be made in the function and arrangement of elements described in an exemplary embodiment without departing from the scope of the invention as set forth in the appended claims.
Claims
1. A phosphate ester comprising phosphate and silicon wherein the phosphate is linked to the silicon by alkyl groups that are bonded via ester bonds with both the phosphate and the silicon.
2. The phosphate ester of claim 1, wherein the alkyl groups are derived from a polyol chosen from pentaerythritol, dipentaerythritol, tripentaerythritol, hexane diol, pentane diol, glycerol, ethylene glycol, propylene glycol, 1,3-propane diol, butane diol, and the like, and combinations thereof.
3. The phosphate ester of claim 1, wherein the phosphate ester has a formula:
[(R3)Phosphate]y [(R^S R2)^, where R1 is any diol or polyol or combination thereof, R2 is any alkyl, aromatic, alkoxy, polyhydroxy, or phenoxy group, R3 is tripropylene glycol butyl ether, heptanol, hexanol, propylene glycol methyl ether (PGME), dipropylene glycol methyl ether, di-propylene glycol propyl ether, di-propylene glycol butyl ether, butanol, pentanol, octanol, decanol, dodecanol or hydroxyl or any combination thereof, n is 1, 2, 3, or 4, and x/y is a value between about 1 to about 200.
4. The phosphate ester of claim 1, wherein the silicon and the phosphate are present at a mole ratio of from about 1 : 1 Si:P to about 200: 1 Si:P.
5. A phosphate-comprising dopant comprising a phosphate-and-silicon network wherein a phosphate and silicon are connected via Si-O-alkyl group-O-P linkages.
6. The phosphate-comprising dopant of claim 5, wherein alkyl groups of the Si- O-alkyl group-O-P linkages are derived from a polyol chosen from pentaerythritol, dipentaerythritol, tripentaerythritol, hexane diol, pentane diol, glycerol, ethylene glycol, propylene glycol, 1,3-propane diol, butane diol, and the like, and combinations thereof.
7. The phosphate-comprising dopant of claim 5, wherein the silicon and the phosphate are present in the phosphate-and-silicon network at a mole ratio of from about 1 : 1 Si:P to about 200: 1 Si:P.
8. The phosphate-comprising dopant of claim 5, further comprising a solvent.
9. The phosphate-comprising dopant of claim 8, wherein the solvent is chosen from propylene glycol methyl ether (PGME), propylene glycol monoether acetate
(PGMEA), l-methoxy-2-propanol, propyleneglycol dimethyl ether, dipropyleneglycol butyl ether, dipropyleneglycol butyl ether acetate, tetrapropyleneglycol butyl ether, tripropylene glycol butyl ether, hexanol, heptanol, and combinations thereof.
10. The phosphate-comprising dopant of claim 5, wherein the phosphate - comprising dopant comprises less than 50 ppb of transition metals.
11. A method of fabricating a phosphate-comprising dopant, the method comprising the steps of:
providing P2O5; and
transesterifying the P2O5 with a polyol-substituted silicon monomer to form a phosphate-comprising ester or reacting the P2O5 with a polyol to form a product and transesterifying the product with a silicon monomer to form a phosphate-comprising ester.
12. The method of claim 1 1, wherein the transesterifying the P2O5 with the polyol-substituted silicon monomer comprises transesterifying an orthosilicate with a polyol to produce the polyol-substituted silicon monomer.
13. The method of claim 12, wherein the transesterifying the orthosilicate with the polyol comprises transesterifying the orthosilicate with the polyol chosen from pentaerythritol, dipentaerythritol, tripentaerythritol, hexane diol, pentane diol, glycerol, ethylene glycol, propylene glycol, 1,3-propane diol, butane diol, and combinations thereof.
14. The method of claim 12, wherein the transesterifying the orthosilicate with the polyol comprises transesterifying tetraethylorthosilicate with the polyol.
15. The method of claim 1 1, wherein the step of reacting the P2O5 with the polyol comprises reacting the P2O5 with the polyol chosen from pentaerythritol, dipentaerythritol, tripentaerythritol, hexane diol, pentane diol, glycerol, ethylene glycol, propylene glycol, 1,3-propane diol, butane diol, and combinations thereof.
16. The method of claim 1 1, wherein the transesterifying the product with the silicon monomer comprises transesterifying the product with the silicon monomer having a formula:
17. The method of claim 11, wherein the transesterifying the product with the silicon monomer comprises transesterifying the product with tetraethylorthosilicate.
18. The method of claim 1 1, wherein the transesterifying the P2O5 with the polyol-substituted silicon monomer to form a phosphate-comprising ester or reacting the P2O5 with the polyol to form the product and transesterifying the product with the silicon monomer to form a phosphate-comprising ester comprise forming a phosphate-comprising ester having a formula:
[(R3)Phosphate]y [(R^S R2)^, where R1 is any diol or polyol or combination thereof, R2 is any alkyl, aromatic, alkoxy, polyhydroxy, or phenoxy group, R3 is tripropylene glycol butyl ether, heptanol, hexanol, propylene glycol methyl ether (PGME), dipropylene glycol methyl ether, di-propylene glycol propyl ether, di-propylene glycol butyl ether, butanol, pentanol, octanol, decanol, dodecanol or hydroxyl or any combination thereof, n is 1, 2, 3, or 4, and x/y is equal to a value between about 1 to about 200.
19. The method of claim 1 1, further comprising the step of adding a solvent to the P2O5, the polyol-substituted silicon monomer, or a mixture thereof.
20. The method of claim 1 1, wherein the silicon monomer is a terra-, tri-, di-, or mono-ester of ethanol or methanol and a silicate.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201161527245P | 2011-08-25 | 2011-08-25 | |
US61/527,245 | 2011-08-25 |
Publications (3)
Publication Number | Publication Date |
---|---|
WO2013028689A2 true WO2013028689A2 (en) | 2013-02-28 |
WO2013028689A3 WO2013028689A3 (en) | 2013-05-10 |
WO2013028689A4 WO2013028689A4 (en) | 2013-07-25 |
Family
ID=47747068
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2012/051719 WO2013028689A2 (en) | 2011-08-25 | 2012-08-21 | Phosphate esters, phosphate-comprising dopants, and methods for fabricating phosphate-comprising dopants using silicon monomers |
Country Status (2)
Country | Link |
---|---|
TW (1) | TW201311711A (en) |
WO (1) | WO2013028689A2 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110526939A (en) * | 2019-08-28 | 2019-12-03 | 衢州市求是科技联合会 | Alkoxy oligomerisation phosphoric acid ethylene ester metal salt and its preparation method and application |
JP2021143139A (en) * | 2020-03-11 | 2021-09-24 | 国立研究開発法人産業技術総合研究所 | Method for producing phosphoester compound |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4243427A (en) * | 1977-11-21 | 1981-01-06 | Trw Inc. | High concentration phosphoro-silica spin-on dopant |
US5070171A (en) * | 1990-06-27 | 1991-12-03 | Siltech Inc. | Phosphated silicone polymers |
US6695903B1 (en) * | 1999-03-11 | 2004-02-24 | Merck Patent Gmbh | Dopant pastes for the production of p, p+, and n, n+ regions in semiconductors |
-
2012
- 2012-08-21 WO PCT/US2012/051719 patent/WO2013028689A2/en active Application Filing
- 2012-08-24 TW TW101130880A patent/TW201311711A/en unknown
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4243427A (en) * | 1977-11-21 | 1981-01-06 | Trw Inc. | High concentration phosphoro-silica spin-on dopant |
US5070171A (en) * | 1990-06-27 | 1991-12-03 | Siltech Inc. | Phosphated silicone polymers |
US6695903B1 (en) * | 1999-03-11 | 2004-02-24 | Merck Patent Gmbh | Dopant pastes for the production of p, p+, and n, n+ regions in semiconductors |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110526939A (en) * | 2019-08-28 | 2019-12-03 | 衢州市求是科技联合会 | Alkoxy oligomerisation phosphoric acid ethylene ester metal salt and its preparation method and application |
CN110526939B (en) * | 2019-08-28 | 2022-02-15 | 衢州市求是科技联合会 | Alkoxy oligopolyethylene phosphate metal salt and preparation method and application thereof |
JP2021143139A (en) * | 2020-03-11 | 2021-09-24 | 国立研究開発法人産業技術総合研究所 | Method for producing phosphoester compound |
JP7462294B2 (en) | 2020-03-11 | 2024-04-05 | 国立研究開発法人産業技術総合研究所 | Method for producing phosphoric acid ester compound |
Also Published As
Publication number | Publication date |
---|---|
WO2013028689A3 (en) | 2013-05-10 |
WO2013028689A4 (en) | 2013-07-25 |
TW201311711A (en) | 2013-03-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US9799783B2 (en) | Dopant ink composition and method of fabricating a solar cell there from | |
JP6319854B2 (en) | Manufacturing method of solar cell | |
JP2011187894A (en) | Coating liquid for diffusing phosphor dopant, coating film formed by the same, and method for manufacturing solar cell | |
CN102533101B (en) | Paintable diffusing agent composition | |
US8518170B2 (en) | Boron-comprising inks for forming boron-doped regions in semiconductor substrates using non-contact printing processes and methods for fabricating such boron-comprising inks | |
TW200947528A (en) | Methods for forming doped regions in semiconductor substrates using non-contact printing processes and dopant-comprising inks for forming such doped regions using non-contact printing processes | |
CN102859658B (en) | The formation method of diffusing agent composition, impurity diffusion layer and solar cell | |
CN104884685A (en) | Doping media for the local doping of silicon wafers | |
WO2012119684A2 (en) | Metallisation barrier based on aluminium oxide | |
WO2013028689A2 (en) | Phosphate esters, phosphate-comprising dopants, and methods for fabricating phosphate-comprising dopants using silicon monomers | |
JP5991846B2 (en) | Film-forming composition, diffusing agent composition, method for producing film-forming composition, and method for producing diffusing agent composition | |
US8629294B2 (en) | Borate esters, boron-comprising dopants, and methods of fabricating boron-comprising dopants | |
CN114342101A (en) | Impurity diffusion composition, method for manufacturing semiconductor element using same, and method for manufacturing solar cell | |
US20150126653A1 (en) | Dopant ink compositions for forming doped regions in semiconductor substrates, and methods for fabricating dopant ink compositions | |
TW201417328A (en) | Method of diffusing impurity-diffusing component and method of manufacturing solar cell | |
WO2012144292A1 (en) | Silica-coating-forming composition for use with inkjets, method for forming silica coating, semiconductor device, and solar-cell system | |
WO2012144291A1 (en) | Silica-coating-forming composition for use with inkjets, method for forming silica coating, semiconductor device, and solar-cell system | |
CN113913236B (en) | Free abrasive water-based cutting fluid for large-size silicon wafers and preparation method thereof | |
CN104073157A (en) | Diffusant composition, method for forming impurity diffusion layer, and solar cell |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 12825836 Country of ref document: EP Kind code of ref document: A2 |
|
NENP | Non-entry into the national phase in: |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 12825836 Country of ref document: EP Kind code of ref document: A2 |