CN114783712A - Method for preparing high-resistance embedded resistor by chemically doping carbon - Google Patents
Method for preparing high-resistance embedded resistor by chemically doping carbon Download PDFInfo
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- CN114783712A CN114783712A CN202210452545.0A CN202210452545A CN114783712A CN 114783712 A CN114783712 A CN 114783712A CN 202210452545 A CN202210452545 A CN 202210452545A CN 114783712 A CN114783712 A CN 114783712A
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- resistor
- resistance
- printed circuit
- embedded resistor
- circuit board
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- 238000000034 method Methods 0.000 title claims abstract description 46
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 239000000758 substrate Substances 0.000 claims abstract description 51
- 239000000463 material Substances 0.000 claims abstract description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 66
- 239000000243 solution Substances 0.000 claims description 57
- 238000007747 plating Methods 0.000 claims description 51
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 43
- 238000004519 manufacturing process Methods 0.000 claims description 39
- 239000008367 deionised water Substances 0.000 claims description 38
- 229910021641 deionized water Inorganic materials 0.000 claims description 38
- 239000000126 substance Substances 0.000 claims description 35
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 27
- 230000004913 activation Effects 0.000 claims description 26
- 206010070834 Sensitisation Diseases 0.000 claims description 25
- 230000008313 sensitization Effects 0.000 claims description 25
- 229910001868 water Inorganic materials 0.000 claims description 24
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 22
- 239000007864 aqueous solution Substances 0.000 claims description 22
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 21
- 230000008569 process Effects 0.000 claims description 21
- 239000001119 stannous chloride Substances 0.000 claims description 21
- 235000011150 stannous chloride Nutrition 0.000 claims description 21
- 238000002791 soaking Methods 0.000 claims description 19
- 239000002390 adhesive tape Substances 0.000 claims description 13
- 150000002500 ions Chemical class 0.000 claims description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 230000007062 hydrolysis Effects 0.000 claims description 12
- 238000006460 hydrolysis reaction Methods 0.000 claims description 12
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 claims description 12
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 11
- 239000008139 complexing agent Substances 0.000 claims description 11
- 238000000059 patterning Methods 0.000 claims description 11
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 10
- 238000000137 annealing Methods 0.000 claims description 10
- 238000000151 deposition Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- UCMIRNVEIXFBKS-UHFFFAOYSA-N beta-alanine Chemical compound NCCC(O)=O UCMIRNVEIXFBKS-UHFFFAOYSA-N 0.000 claims description 8
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 8
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 7
- 229910001096 P alloy Inorganic materials 0.000 claims description 7
- 239000007853 buffer solution Substances 0.000 claims description 7
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 6
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 235000011056 potassium acetate Nutrition 0.000 claims description 6
- 239000001632 sodium acetate Substances 0.000 claims description 6
- 235000017281 sodium acetate Nutrition 0.000 claims description 6
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 5
- 229910002666 PdCl2 Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 5
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 5
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229940000635 beta-alanine Drugs 0.000 claims description 4
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 4
- 239000004310 lactic acid Substances 0.000 claims description 4
- 235000014655 lactic acid Nutrition 0.000 claims description 4
- BJEPYKJPYRNKOW-UHFFFAOYSA-N malic acid Chemical compound OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 239000001509 sodium citrate Substances 0.000 claims description 4
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 4
- 229960000583 acetic acid Drugs 0.000 claims description 3
- 239000012362 glacial acetic acid Substances 0.000 claims description 3
- 238000012360 testing method Methods 0.000 abstract description 18
- 229910018104 Ni-P Inorganic materials 0.000 abstract description 12
- 229910018536 Ni—P Inorganic materials 0.000 abstract description 12
- 230000003071 parasitic effect Effects 0.000 abstract description 7
- 238000002360 preparation method Methods 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 4
- 229910018487 Ni—Cr Inorganic materials 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract description 2
- 229910002058 ternary alloy Inorganic materials 0.000 abstract description 2
- 238000007385 chemical modification Methods 0.000 abstract 1
- 238000004891 communication Methods 0.000 abstract 1
- 239000011347 resin Substances 0.000 abstract 1
- 229920005989 resin Polymers 0.000 abstract 1
- 230000008054 signal transmission Effects 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 28
- 238000001994 activation Methods 0.000 description 23
- 125000004429 atom Chemical group 0.000 description 20
- 239000010409 thin film Substances 0.000 description 20
- 239000000523 sample Substances 0.000 description 18
- 238000007772 electroless plating Methods 0.000 description 17
- 238000005406 washing Methods 0.000 description 16
- 238000005238 degreasing Methods 0.000 description 12
- 238000003475 lamination Methods 0.000 description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- 230000003213 activating effect Effects 0.000 description 10
- 238000004140 cleaning Methods 0.000 description 10
- 239000010408 film Substances 0.000 description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 239000003638 chemical reducing agent Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 229910052763 palladium Inorganic materials 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- 239000001488 sodium phosphate Substances 0.000 description 5
- 229910000162 sodium phosphate Inorganic materials 0.000 description 5
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 5
- 238000004506 ultrasonic cleaning Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 230000003301 hydrolyzing effect Effects 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 230000001235 sensitizing effect Effects 0.000 description 4
- 239000000872 buffer Substances 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 238000012935 Averaging Methods 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910011208 Ti—N Inorganic materials 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005672 electromagnetic field Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
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- 238000003756 stirring Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
- H01C17/06—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base
- H01C17/075—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base by thin film techniques
- H01C17/14—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base by thin film techniques by chemical deposition
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1603—Process or apparatus coating on selected surface areas
- C23C18/1605—Process or apparatus coating on selected surface areas by masking
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1689—After-treatment
- C23C18/1692—Heat-treatment
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
- C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
- C23C18/1837—Multistep pretreatment
- C23C18/1841—Multistep pretreatment with use of metal first
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
- C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
- C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
- H01C17/006—Apparatus or processes specially adapted for manufacturing resistors adapted for manufacturing resistor chips
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
- H05K3/181—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating
- H05K3/182—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating characterised by the patterning method
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemically Coating (AREA)
Abstract
The invention discloses a method for preparing a high-resistance embedded resistor by chemically doping carbon. The resistance additive is adopted to provide a C source doped Ni-P film for chemical modification, so that the Ni-P-C ternary alloy high-resistance material deposited on the resin substrate is prepared. Tests show that the square resistance of the material is as high as more than 400 omega, and the aim of controlling the preparation error within 10 percent is fulfilled by the method of assisting the resistor to be monitored online. The method disclosed by the invention effectively solves the problems of small resistance value and unstable functional value of the conventional metal resistors such as Ni-P, Ni-Cr and the like, and reduces the loss and parasitic effect of signal transmission under high-frequency communication.
Description
Technical Field
The invention relates to the technical field of electronic materials and electronic components, in particular to an embedded thin film resistor material and a preparation method thereof.
Background
The speed, function, performance and portability of electronic products are continuously improved, the requirements for miniaturization and high integration of the packaging size of an integrated circuit are higher and higher, and the requirements are in order to meet the contradiction between the number of elements in the integrated circuit and the sharp increasing trend of embedded passive elements and the limited area of a printed circuit board. One solution is to embed these passive components in the printed circuit board. The embedded passive component has a small surface space, low mounting cost, high signal quality, and reduced parasitic effects by minimizing the number of pads and wiring distance. Embedded Thin Film Resistors (ETFR) are one of the Embedded passive components, and play an important role in saving the space of Printed Circuit Boards (PCBs).
At present, the manufacturing routes of the integrated resistor include screen printing metal thick film resistor, etching metal thin film resistor, magnetron sputtering thin film resistor, chemical plating metal thin film resistor, and aerosol jet printing. Typically Ti-N, Ni-Cr, Ta-N, Ni-P and Ta-Si, have been chosen as integrated resistive materials due to their high reliability, lower TCR and adaptability to PCB manufacturing processes. The production of the Ni-Cr buried resistance material is adjusted by a plurality of etching processes, the resistance error is higher than 15%, and a high-precision resistor cannot be produced; Ni-P has attracted considerable attention due to its particularly high resistance stability under high frequency and pulse heating, excellent mechanical flexibility on flexible polyimide substrates, and simplicity of its manufacturing procedure, but Ni-P thin film materials have limited application in embedded resistors with resistance values exceeding 10k Ω due to their low sheet resistance. In order to improve the influence of the parasitic effect of the resistor at high frequencies, the resistor width should be as small as possible, and thus the sheet resistance value of the integrated resistive material should be as large as possible. Therefore, the performance of Ni-P alloy as ETFR material still needs to be further improved, such as the requirement of lower TCR, high resistance and high precision thin film resistance.
Based on the above requirements for high sheet resistance, the invention provides a method for preparing a high-resistance embedded resistor by chemically doping carbon. The resistance of Ni-P is increased by using a resistance additive to promote the formation of a ternary alloy of Ni-P-C. The simulation of the high-resistance Ni-P-C through the HFSS electromagnetic field has obvious advantages in the aspect of solving the parasitic effect, so that the method has good prospects in the high-frequency application scene.
The invention content is as follows:
the invention aims to solve the technical problem that the application of the existing embedded thin film Ni-P resistor material in an embedded resistor with the resistance value exceeding 10k omega is limited due to low sheet resistance, and provides a method for preparing a high-resistance embedded resistor by chemically doping carbon. The radius of the C atoms is small, the Ni crystal lattices are entered in a form of interstitial atoms, the problem that the formed Ni-P film layer is unstable in softness and electrical property is solved along with the increase of the C elements, the amorphous components of the film can be increased by realizing the increase of the C elements, disordered atomic arrangement is increased, the sheet resistance value of the film is increased, the high sheet resistance is obtained, the effects of reducing resistance errors and the like are finally realized, and the requirement of reducing parasitic effects under the high-frequency and high-speed conditions is met.
In order to solve the technical problem, the invention provides a method for preparing a high-resistance embedded resistor by chemically doping carbon, which comprises the following steps:
step 1: printed circuit patterning
Manufacturing a resistance pattern on the surface of the copper-clad plate by adopting a printed circuit manufacturing process to obtain a patterned printed circuit board;
step 2: sensitization/hydrolysis of stannous chloride
Soaking the patterned printed circuit board in stannous chloride aqueous solution for sensitization, soaking the patterned printed circuit board in deionized water for hydrolysis after sensitization, and depositing a layer of stannous salt gel Sn slightly soluble in water on the surface of the substrate of the patterned printed circuit board2(OH)3Cl；
And 3, step 3: palladium chloride activation
Sn is deposited on the surface of the base material2(OH)3Soaking the Cl patterned printed circuit board in PdCl2In aqueous solution, to make Sn2(OH)3Pd in palladium chloride solution by Cl2+Reducing ions into Pd atoms and depositing the Pd atoms on the surface of the base material of the graphical printed circuit board so as to form a chemical plating activation center;
and 4, step 4: graphics fabrication
Sticking an adhesive tape on the surface of the graphical printed circuit board processed in the step (3), covering a region where the embedded resistor is not required to be manufactured by using a resistor graphical adhesive tape, and exposing a manufacturing region of the embedded resistor;
and 5: chemical plating embedded resistor
Carrying out chemical plating in the embedded resistor manufacturing area to obtain chemical plating solution with the nickel content of 52-82%, the phosphorus content of 8-29%, the carbon content of 4-11% and the oxygen content of 3.5-8%, wherein the chemical plating solution comprises the following components in the formula: 10-55g/L of nickel sulfate or nickel chloride, 10-50 g/L of sodium hypophosphite, 2-20 g/L of buffer solution, 5-40 g/L of complexing agent and 0-4 ml/L of resistance regulator, wherein when the plating solution is prepared, the pH value is regulated to be 4.5-6.5 by adopting the pH value regulator, and the temperature is kept to be 70-90 ℃ in the using process of the plating solution;
step 6: annealing of
And (4) carrying out heat treatment on the carbon-doped nickel-phosphorus alloy embedded resistor obtained in the step (5) at the temperature of 120-200 ℃ for more than 30 minutes to obtain the embedded resistor with stable resistance.
Preferably, the buffer in step 5 is at least one of sodium acetate and potassium acetate.
Preferably, in step 5, the complexing agent is at least one of sodium citrate, succinic acid, thiourea, DL malic acid or lactic acid, and triethylamine.
Preferably, in step 5, the resistance value regulator is at least one of diethylenetriamine or beta-alanine.
Preferably, in step 5, the PH adjuster is at least one of ammonia water, sodium hydroxide, potassium hydroxide, and glacial acetic acid.
As a preferable mode, the annealing treatment in the step 6 is specifically to put the resistor cleaned by deionized water into an oven to be dried until the surface is dried.
It is noted that since tin is a polyvalent cation, SnCl is produced2In the case of aqueous solutions, a certain amount of concentrated hydrochloric acid is added to prevent SnCl2Sn in aqueous solution2+Is oxidized to Sn4+(ii) a Preparation of PdCl2When the PdCl is difficult to dissolve in water, a certain amount of concentrated hydrochloric acid is also required to be added to increase PdCl2The solubility of (2).
In the above technical scheme: the pH value buffer is sodium acetate or potassium acetate, the pH value of the constant plating solution is in a set range, the complexing agent is one or more of citric acid, succinic acid, thiourea, DL malic acid or lactic acid, and the pH value buffer is used for complexing Ni2+Releasing a fixed amount of Ni in the electroless plating solution2+(ii) a The pH value regulator is one or more of ammonia water, sodium hydroxide or potassium hydroxide and is used for regulating the pH value to a required value; the resistance regulator is one or more of diethylenetriamine or beta-alanine, and the function of the resistance regulator is to enable the electroless plating solution to form a carbon-doped Ni-P thin film.
The plating solution is added with a resistance regulator to ensure that the non-metallic element carbon with small atomic radius can improve the Ni-P film structure, thereby improving the resistivity of the resistance layer material, and the square resistance of the resistance layer material is increased along with the increase of the content of the resistance regulator in the formula of the plating solution.
The embedded resistance material prepared by the invention is of a porous structure, contains 52-82% of nickel, 8-29% of phosphorus, 4-11% of carbon and 3.5-8% of oxygen, is a carbon-doped nickel-phosphorus thin film deposited by a chemical plating method and an online monitoring technology, has the characteristics of large square resistance (the highest 731 omega/sq), good resistance stability and the like through an experimental surface, makes experimental promotion for modification research of nickel-phosphorus resistors, is simple in manufacturing process, and is easy to popularize in printed circuit enterprises.
Description of the drawings:
FIG. 1 is a flow chart of a method for fabricating a high resistance embedded resistor by chemical doping carbon according to an embodiment of the present invention;
FIGS. 2(a-e) are SEM images of a high-resistance embedded resistance material prepared by chemically doping carbon under the condition that the concentration of diethylenetriamine is 0,1,2,3 and 4mL/L respectively, and (f) is a side view of diethylenetriamine 2 mL/L; the difference of the sizes of the porous structure crystal packets after the chemical doping of carbon can be obviously seen.
FIG. 3 is an EDS diagram of the embedded thin film resistive material prepared by the present invention. The abscissa is energy, in keV; the ordinate is intensity, and the unit is C/S; the main components in the figure are Ni, P and C elements.
FIG. 4 is a graph showing the variation of the square resistance value of the embedded thin film resistor material with the content of the resistance regulator. The abscissa represents the content of diethylenetriamine, the unit is mL/L, and the ordinate represents the resistance value of the square resistor to be omega/sq.
FIG. 5 is SEM images after and before lamination of the embedded thin film resistor material;
FIG. 6 is a SEM image of Temperature Coefficient of Resistance (TCR) of embedded thin film resistor material with temperature variation and TCR after testing;
fig. 7 is a graph showing a variation curve of a simulation result of the parasitic resistance of the parasitic resistances of the embedded resistor and the chip resistor.
The specific implementation mode is as follows:
the embodiment provides a method for preparing a high-resistance embedded resistor by chemically doping carbon, which comprises the following steps:
step 1: printed circuit patterning
Manufacturing a resistance pattern on the surface of the copper-clad plate by adopting a printed circuit manufacturing process to obtain a patterned printed circuit board;
step 2: sensitization/hydrolysis of stannous chloride
Soaking the patterned printed circuit board in stannous chloride aqueous solution for sensitization, soaking the patterned printed circuit board in deionized water for hydrolysis after sensitization, and depositing a layer of stannous salt gel Sn slightly soluble in water on the surface of the substrate of the patterned printed circuit board2(OH)3Cl；
And 3, step 3: palladium chloride activation
Sn is deposited on the surface of the base material2(OH)3Soaking the Cl graphical printed circuit board in palladium chloride PdCl2In aqueous solution, to make Sn2(OH)3Pd in palladium chloride solution by Cl2+Reducing ions into Pd atoms and depositing the Pd atoms on the surface of the base material of the graphical printed circuit board so as to form a chemical plating activation center;
and 4, step 4: graphics fabrication
Sticking an adhesive tape on the surface of the graphical printed circuit board processed in the step 3, and covering a region where the embedded resistor is not required to be manufactured by using a resistor graphical adhesive tape to expose a manufacturing region of the embedded resistor;
and 5: chemical plating embedded resistor
Carrying out chemical plating in the embedded resistor manufacturing area to obtain chemical plating solution with the nickel content of 52-82%, the phosphorus content of 8-29%, the carbon content of 4-11% and the oxygen content of 3.5-8%, wherein the chemical plating solution comprises the following components in concentration: 10-55g/L of nickel sulfate or nickel chloride, 10-50 g/L of sodium hypophosphite, 2-20 g/L of buffer solution, 5-40 g/L of complexing agent and 0-4 ml/L of resistance value regulator, wherein when the plating solution is prepared, the pH value is regulated to be 4.5-6.5 by adopting the pH value regulator, and the temperature is kept to be 70-90 ℃ in the using process of the plating solution;
and in the step 5, the buffer solution is at least one of sodium acetate or potassium acetate.
In the step 5, the complexing agent is at least one of sodium citrate, succinic acid, thiourea, DL malic acid or lactic acid and triethylamine.
In the step 5, the resistance value regulator is at least one of diethylenetriamine or beta-alanine.
And in the step 5, the pH regulator is at least one of ammonia water, sodium hydroxide, potassium hydroxide and glacial acetic acid.
Step 6: annealing
And (4) carrying out heat treatment on the carbon-doped nickel-phosphorus alloy embedded resistor obtained in the step (5) at the temperature of 120-200 ℃ for more than 30 minutes to obtain the embedded resistor with stable resistance.
The annealing treatment is to put the resistor cleaned by deionized water into an oven to be dried until the surface is dried.
Comparative example
The embedded thin film resistor is prepared by adopting an embedded resistor preparation process provided by MacDermid Incorporated as follows:
(1) alkaline degreasing of a substrate:
the oil removing formula comprises: 35g/L of sodium carbonate, 50g/L of sodium phosphate and 25g/L of sodium hydroxide;
the first step is as follows: placing the prepared chemical oil removal solution in a constant-temperature water bath, and adjusting the temperature of the water bath to be 50-60 ℃;
the second step: after the temperature rises to a preset temperature, putting the sample into an oil removing solution, putting a beaker of the oil removing solution into an ultrasonic cleaning machine, and ultrasonically cleaning for 5-15 min;
the third step: after oil removal, taking out the substrate, washing the two sides of the sample by deionized water for 3 times, putting the sample into a beaker with deionized water, and ultrasonically cleaning for 2 min;
(2) stannous chloride sensitization hydrolysis
Soaking the printed circuit board after alkaline degreasing in a stannous chloride aqueous solution for sensitization, wherein the sensitization process conditions are as follows:
TABLE 1 sensitization fluids
| Stannous chloride (SnCl)2.H2O) | 40g/L |
| Concentrated hydrochloric acid | 10ml/L |
| Temperature of | At room temperature |
| Time | 4min |
Taking out the sensitized substrate, placing in deionized water, hydrolyzing for 3min to obtain stannous salt gel Sn slightly soluble in water2(OH)3Cl and is uniformly deposited on the surface of the substrate, Sn2(OH)3The Cl is used as a reducing agent in the activation treatment of Pd of palladium chloride solution serving as an activating agent2+The ions are reduced to Pd atoms and attached to the substrate surface of the patterned printed circuit board, thereby forming electroless plating activation centers.
And finally, taking out the sensitized and hydrolyzed substrate, and washing the substrate twice by using deionized water.
(3) Activation of palladium chloride:
soaking the substrate cleaned by the deionized water in the previous step in a palladium chloride aqueous solution for reduction reaction, and carrying out Sn2+Ion-exchange of Pd in aqueous solution of palladium chloride2+The ions are reduced into Pd atoms, and the Pd atoms are attached to the surface of the base material of the patterned printed circuit board, so that an electroless plating activation center is formed. The activation process conditions are shown in table 2:
TABLE 2 activating solution
| Palladium chloride | 0.5g/L |
| Concentrated hydrochloric acid | 10ml/L |
| Temperature of | At room temperature |
| Time | 3min |
(4) Electroless plating of resistive materials
The substrate is placed in a plating solution, a water bath kettle is used for stabilizing the temperature of the plating solution, and the stirring speed is 100-200r/min to facilitate the reaction of the plating solution. The process conditions are shown in Table 3:
table 3 process conditions for electroless plating of embedded thin film Ni-P resistive material:
| nickel sulfate | 33g/L |
| Sodium hypophosphite | 40g/L |
| Buffer (sodium acetate) | 10g/L |
| Complexing agent (citric acid) | 23.4g/L |
| Temperature (Water bath) | 90℃ |
| Time | 10min |
(5) Deionized water flushing
And after chemically plating the chemically plated resistor material for 10min, washing the embedded resistor by using deionized water, and then drying for 30min by using a vacuum drying box at 30 ℃.
(6) Testing square resistance
Embedding resistors in the steps, testing the square resistors by using a four-probe tester, testing different positions at least three times, and averaging, wherein the resistance value of the square resistor is 17.1 omega/sq.
And (3) placing the resistance material at 120 ℃ for heat treatment for 30min, wherein the square resistance of the resistance is 17.1 omega/sq.
As can be seen from the comparative embodiment, the sheet resistance of the embedded resistor prepared by the embedded resistor preparation process prepared by adopting the basic formula is only 17.1 omega/sq.
Example 1
Epoxy resin in a 0.2mm double-sided copper-clad plate is used as a base material to be used as a chemical plating insulating base plate,
step 1: patterning of printed circuits
Manufacturing a resistance pattern on the surface of the copper-clad plate by adopting a printed circuit manufacturing process to obtain a patterned printed circuit board;
alkaline degreasing of the substrate after patterning of the printed circuit:
the oil removing formula comprises: 35g/L of sodium carbonate, 50g/L of sodium phosphate and 25g/L of sodium hydroxide;
the first step is as follows: placing the prepared chemical degreasing solution in a constant-temperature water bath, and adjusting the temperature of the water bath to be 50 ℃;
the second step is that: after the temperature rises to the preset temperature, putting the sample into the oil removing solution, putting the beaker of the oil removing solution into an ultrasonic cleaning machine, and ultrasonically cleaning for 10 min;
the third step: after oil removal, taking out the substrate, washing the two sides of the sample for 3 times by using deionized water, putting the sample into a beaker with the deionized water, and ultrasonically cleaning for 2 min;
step 2: stannous chloride sensitization hydrolysis
Soaking the printed circuit board after alkaline degreasing in stannous chloride aqueous solution for sensitization,
the sensitization process conditions are shown in table 4:
TABLE 4 sensitizing solution
| Stannous chloride (SnCl)2.H2O) | 40g/L |
| Concentrated hydrochloric acid | 10ml/L |
| Temperature of | At room temperature |
| Time | 4min |
Taking out the sensitized substrate, placing in deionized water, hydrolyzing for 3min to obtain stannous salt gel Sn slightly soluble in water2(OH)3Cl and is uniformly deposited on the surface of the substrate, Sn2(OH)3The Cl is used as a reducing agent in the activation treatment of Pd of palladium chloride solution serving as an activating agent2+The ions are reduced to Pd atoms and attached to the substrate surface of the patterned printed circuit board, thereby forming electroless plating activation centers.
And finally, taking out the sensitized and hydrolyzed substrate, and washing the substrate twice by using deionized water.
And 3, step 3: activation of palladium chloride:
soaking the substrate cleaned by the deionized water in the previous step in a palladium chloride aqueous solution for reduction reaction, and carrying out Sn2+Ion-exchange of Pd in aqueous solution of palladium chloride2+The ions are reduced to Pd atoms, and the Pd atoms are attached to the surface of the substrate of the patterned printed circuit board, so that electroless plating activation centers are formed.
The activation process conditions are shown in table 5:
TABLE 5 activating solution
| Palladium chloride | 0.5g/L |
| Concentrated hydrochloric acid | 10ml/L |
| Temperature of | At room temperature |
| Time | 3min |
And 4, step 4: graphics fabrication
Sticking an adhesive tape on the surface of the graphical printed circuit board processed in the step 3, and covering a region where the embedded resistor is not required to be manufactured by using a resistor graphical adhesive tape to expose a manufacturing region of the embedded resistor;
and 5: chemical plating embedded resistor
Chemical plating is carried out in the embedded resistor manufacturing area, the PH value is adjusted to 4.5 by adopting ammonia water as a PH value regulator when the plating solution is prepared,
the process conditions used in step (5) are shown in table 6:
TABLE 6 Process conditions for electroless plating of embedded thin film resistor materials
| Nickel sulfate | 33g/L |
| Sodium hypophosphite | 40g/L |
| Buffer (sodium acetate) | 10g/L |
| Complexing agent (citric acid) | 23.4g/L |
| Resistance regulator (diethylenetriamine) | 0.5mL/L |
| Temperature (Water bath) | 90℃ |
| Time | 10min |
And (3) chemically plating the resistance material chemically plated in the step (5) for 10min, washing the embedded resistor by using deionized water, washing the embedded resistor by using the deionized water, and drying the embedded resistor for 30min at the temperature of 30 ℃ by using a vacuum drying box.
And 6: annealing of
And (4) carrying out heat treatment on the carbon-doped nickel-phosphorus alloy embedded resistor obtained in the step (5) at the temperature of 120 ℃ for more than 30 minutes to obtain the embedded resistor with stable resistance.
And 7: testing
Then, the embedded resistor material is tested for the square resistor by using a four-probe tester and is subjected to at least three times of testing at different positions to obtain an average value, the resistance value of the square resistor is 609 omega/sq.
As can be seen from the above specific example 1, the sheet resistance of the embedded resistor material prepared by the method of the present invention is much larger than that of the embedded resistor material prepared by the embedded resistor provided by the basic formula, and the resistance is stable after heat treatment (the thermal deviation is less than 6%). The materials were tested using a lamination test, the lamination test process is shown in table 7 below:
table 7 lamination test process conditions
The square resistance value is 563 omega/sq, which shows that the square resistance of the embedded resistor prepared by the invention is slightly influenced by lamination. Meanwhile, the adhesive tape method is used for checking the binding force of the prepared embedded resistor, and the surface binding force is good.
Example 2
Step 1: printed circuit patterning
Manufacturing a resistance pattern on the surface of the copper-clad plate by adopting a printed circuit manufacturing process to obtain a patterned printed circuit board;
alkaline degreasing of the substrate after patterning of the printed circuit:
the oil removing formula comprises: 35g/L of sodium carbonate, 50g/L of sodium phosphate and 25g/L of sodium hydroxide;
the first step is as follows: placing the prepared chemical oil removal solution in a constant-temperature water bath, and adjusting the temperature of the water bath to be 50 ℃;
the second step is that: after the temperature rises to the preset temperature, putting the sample into the oil removing solution, putting the oil removing solution beaker into an ultrasonic cleaning machine, and ultrasonically cleaning for 10 min;
the third step: after oil removal, taking out the substrate, washing the two sides of the sample by deionized water for 3 times, putting the sample into a beaker with deionized water, and ultrasonically cleaning for 2 min;
step 2: stannous chloride sensitization hydrolysis
Soaking the printed circuit board after alkaline degreasing in stannous chloride aqueous solution for sensitization,
the sensitization process conditions are shown in table 8:
TABLE 8 sensitizing solution
| Stannous chloride (SnCl)2.H2O) | 40g/L |
| Concentrated hydrochloric acid | 10ml/L |
| Temperature of | At room temperature |
| Time | 4min |
Taking out the sensitized substrate, placing in deionized water, hydrolyzing for 3min to obtain stannous salt gel Sn slightly soluble in water2(OH)3Cl and is uniformly deposited on the surface of the substrate, Sn2(OH)3The Cl is taken as a reducing agent, and the Pd of the palladium chloride solution of an activating agent is used in the activation treatment2+The ions are reduced into Pd atoms and attached to the surface of the substrate of the patterned printed circuit board, thereby forming a chemicalAnd plating an activation center.
And finally, taking out the sensitized and hydrolyzed substrate, and washing the substrate twice by using deionized water.
And step 3: activation of palladium chloride:
soaking the substrate cleaned by the deionized water in the previous step in a palladium chloride aqueous solution for reduction reaction, and carrying out Sn2+Ion-exchange of Pd in aqueous solution of palladium chloride2+The ions are reduced into Pd atoms, and the Pd atoms are attached to the surface of the base material of the patterned printed circuit board, so that an electroless plating activation center is formed.
The activation process conditions are shown in table 9:
TABLE 9 activating solutions
| Palladium chloride | 0.5g/L |
| Concentrated hydrochloric acid | 10ml/L |
| Temperature of | At room temperature |
| Time | 3min |
And 4, step 4: graphics fabrication
Sticking an adhesive tape on the surface of the graphical printed circuit board processed in the step (3), covering a region where the embedded resistor is not required to be manufactured by using a resistor graphical adhesive tape, and exposing a manufacturing region of the embedded resistor;
and 5: chemical plating embedded resistor
Chemical plating is carried out in the embedded resistor manufacturing area, when the plating solution is prepared, the pH value is adjusted to be 5.5 by adopting a pH value regulator sodium hydroxide,
the process conditions used in step (5) are shown in table 10:
TABLE 10 Process conditions for electroless plating of embedded thin film resistor materials
| Nickel chloride | 55g/L |
| Sodium hypophosphite | 50/L |
| Buffer solution (Potassium acetate) | 20g/L |
| Complexing agent (succinic acid) | 40g/L |
| Resistance regulator (diethylenetriamine) | 2mL/L |
| Temperature (Water bath) | 85℃ |
| Time | 8min |
And (3) chemically plating the resistance material chemically plated in the step (5) for 8min, washing the embedded resistor by using deionized water, and drying the embedded resistor for 30min at the temperature of 30 ℃ by using a vacuum drying box.
Step 6: annealing
And (4) carrying out heat treatment on the carbon-doped nickel-phosphorus alloy embedded resistor obtained in the step (5) at the temperature of 200 ℃ for more than 30 minutes to obtain the embedded resistor with stable resistance.
And 7: testing
And then testing the embedded resistor material by using a four-probe tester to test the square resistor, and at least testing different positions for three times to obtain an average value, wherein the resistance value of the square resistor is 731 omega/sq.
Example 3
The linear embedded resistor is designed, so that the high-resistance value on-line monitoring can be realized, the wide applicability of the carbon-doped nickel-phosphorus embedded film resistor material is verified, and the influence of lamination on the resistor is verified.
Step 1: printed circuit patterning
Manufacturing a linear resistor pattern on the surface of the copper-clad plate by adopting a printed circuit manufacturing process to obtain a patterned printed circuit board;
alkaline degreasing of the substrate after patterning of the printed circuit:
the oil removing formula comprises: 35g/L of sodium carbonate, 50g/L of sodium phosphate and 25g/L of sodium hydroxide;
the first step is as follows: placing the prepared chemical oil removal solution in a constant-temperature water bath, and adjusting the temperature of the water bath to be 50 ℃;
the second step is that: after the temperature rises to the preset temperature, putting the sample into the oil removing solution, putting the beaker of the oil removing solution into an ultrasonic cleaning machine, and ultrasonically cleaning for 10 min;
the third step: after oil removal, taking out the substrate, washing the two sides of the sample for 3 times by using deionized water, putting the sample into a beaker with the deionized water, and ultrasonically cleaning for 2 min;
and 2, step: sensitization hydrolysis of stannous chloride
Soaking the printed circuit board after alkaline degreasing in stannous chloride aqueous solution for sensitization,
the sensitization process conditions are shown in Table 11:
TABLE 11 sensitizing solution
| Stannous chloride (SnCl)2.H2O) | 40g/L |
| Concentrated hydrochloric acid | 10ml/L |
| Temperature of | At room temperature |
| Time | 4min |
Taking out the sensitized substrate, placing the substrate in deionized water for hydrolysis for 3min to obtain a slightly water-soluble stannous salt gel Sn2(OH)3Cl and is uniformly deposited on the surface of the substrate, Sn2(OH)3The Cl is used as a reducing agent in the activation treatment of Pd of palladium chloride solution serving as an activating agent2+The ions are reduced to Pd atoms and attached to the substrate surface of the patterned printed circuit board, thereby forming electroless plating activation centers.
And finally taking out the sensitized and hydrolyzed substrate and washing the substrate twice by using deionized water.
And 3, step 3: activation of palladium chloride:
soaking the substrate cleaned by the deionized water in the previous step in a palladium chloride aqueous solution for reduction reaction, and carrying out Sn2+Ion-exchange of Pd in aqueous solution of palladium chloride2+The ions are reduced to Pd atoms, and the Pd atoms are attached to the surface of the substrate of the patterned printed circuit board, so that electroless plating activation centers are formed.
The activation process conditions are shown in table 12:
TABLE 12 activating solutions
| Palladium chloride | 0.5g/L |
| Concentrated hydrochloric acid | 10ml/L |
| Temperature of | At room temperature |
| Time | 3min |
And 4, step 4: graphics fabrication
A dry film is pasted on the printed circuit board in the imaging mode after the processing in the step 3, a resistor graph mask is used for exposure, the dry film is removed in the area where the resistor needs to be manufactured after the development, and then the resistance film material is prepared for chemical plating in the next step;
and 5: chemical plating embedded resistor
Chemical plating is carried out in the embedded resistor manufacturing area, a PH value regulator is adopted to regulate the PH value to be 5 when the plating solution is prepared,
the process conditions used in step (5) are shown in table 13:
TABLE 13 Process conditions for electroless plating of embedded thin film resistor materials
And (3) when the voltage of the chemical plating of the resistance material in the step (5) is monitored to be 5.4mv on line by using a keithley2400 Source Meter instrument, washing the embedded resistor by using deionized water, and then drying for 30min by using a vacuum drying box at 30 ℃.
Step 6: annealing
And (4) performing heat treatment on the carbon-doped nickel-phosphorus alloy embedded resistor obtained in the step (5) at the temperature of 160 ℃ for more than 30 minutes to obtain the embedded resistor with stable resistance.
And 7: testing of
The embedded resistor material was then tested for resistance across the embedded resistor using a keithley2400 Source Meter instrument as shown in table 14.
TABLE 14
| Location of the resistor | Omega before lamination | Omega after |
| 1 | 241.6 | 231.376 |
| 2 | 228.432 | 225.325 |
| 3 | 221.035 | 218.025 |
| 4 | 228.189 | 223.197 |
| 5 | 238.752 | 231.357 |
| 6 | 228.052 | 219.354 |
The electrical resistance before and after lamination is shown in fig. 5. After the lamination test is finished, the resistance value of the resistor deposition area is tested by adopting a keithley2400 Source Meter instrument, and as can be seen from fig. 5, the influence of the lamination on the resistance value of the embedded resistor is small as the change of the resistance value of the embedded resistor is small. And the plating layer has no bad phenomena of cracking, peeling and the like, which shows that the lamination has no influence on the appearance of the nickel-phosphorus plating layer.
Example 4
Using an epoxy resin substrate to form a buried resistor on the pattern of the substrate, wherein the preparation process comprises the following steps:
the wide applicability of the carbon-doped nickel-phosphorus embedded film resistor material and the thermal stability of the resistor are verified.
Step 1: printed circuit patterning
Manufacturing a resistance pattern on the surface of the copper-clad plate by adopting a printed circuit manufacturing process to obtain a patterned printed circuit board;
the oil removing formula comprises: 35g/L of sodium carbonate, 50g/L of sodium phosphate and 25g/L of sodium hydroxide;
the first step is as follows: placing the prepared chemical degreasing solution in a constant-temperature water bath, and adjusting the temperature of the water bath to be 50 ℃;
the second step: after the temperature rises to the preset temperature, putting the sample into the oil removing solution, putting the beaker of the oil removing solution into an ultrasonic cleaning machine, and ultrasonically cleaning for 10 min;
the third step: after oil removal, taking out the substrate, washing the two sides of the sample by deionized water for 3 times, putting the sample into a beaker with deionized water, and ultrasonically cleaning for 2 min;
step 2: stannous chloride sensitization hydrolysis
Soaking the printed circuit board after alkaline degreasing in stannous chloride aqueous solution for sensitization,
the sensitization process conditions are shown in Table 15:
TABLE 15 sensitizing solution
| Stannous chloride (SnCl)2.H2O) | 40g/L |
| Concentrated hydrochloric acid | 10ml/L |
| Temperature of | At room temperature |
| Time | 4min |
Taking out the sensitized substrate, placing in deionized water, hydrolyzing for 3min to obtain stannous salt gel Sn slightly soluble in water2(OH)3Cl and is uniformly deposited on the surface of the substrate, Sn2(OH)3The Cl is taken as a reducing agent, and the Pd of the palladium chloride solution of an activating agent is used in the activation treatment2+The ions are reduced to Pd atoms and attached to the substrate surface of the patterned printed circuit board, thereby forming electroless plating activation centers.
And finally taking out the sensitized and hydrolyzed substrate and washing the substrate twice by using deionized water.
And step 3: activation of palladium chloride:
soaking the substrate cleaned by the deionized water in the previous step in a palladium chloride aqueous solution for reduction reaction, and carrying out Sn2+Ionic liquid of palladium chloridePd in (2)2+The ions are reduced into Pd atoms, and the Pd atoms are attached to the surface of the base material of the patterned printed circuit board, so that an electroless plating activation center is formed.
The activation process conditions are shown in table 16:
TABLE 16 activating solutions
| Palladium chloride | 0.5g/L |
| Concentrated hydrochloric acid | 10ml/L |
| Temperature of | At room temperature |
| Time | 3min |
And 4, step 4: graphics fabrication
Sticking an adhesive tape on the surface of the graphical printed circuit board processed in the step 3, and covering a region where the embedded resistor is not required to be manufactured by using a resistor graphical adhesive tape to expose a manufacturing region of the embedded resistor;
and 5: chemical plating embedded resistor
Carrying out chemical plating in the embedded resistor manufacturing area, and adjusting the pH value to be 6 by adopting ammonia water as a pH value regulator when the plating solution is prepared;
the process conditions used in step (5) are shown in table 17:
TABLE 17 Process conditions for electroless plating of embedded thin film resistor materials
| Nickel chloride | 40g/L |
| Sodium hypophosphite | 35.2/L |
| Buffer solution (Potassium acetate) | 14g/L |
| Complexing agent (sodium citrate) | 36g/L |
| Resistance value regulator (diethylenetriamine) | 4mL/L |
| Temperature (Water bath) | 90℃ |
| Monitoring voltage | 3.4min |
And (4) chemically plating the chemically plated resistor material in the step (5) for 8min, washing the embedded resistor by using deionized water, and drying the embedded resistor for 30min by using a vacuum drying box at the temperature of 30 ℃.
And 6: annealing of
And (3) carrying out heat treatment on the carbon-doped nickel-phosphorus alloy embedded resistor obtained in the step (5) for more than 30 minutes at the temperature of 120 ℃ to obtain the embedded resistor with stable resistance.
And 7: testing of
The resistance value change of the resistance in the deposition area of the embedded resistor caused by the change of the temperature from 20 ℃ to 120 ℃ is tested by adopting a keithley2400 Source Meter instrument, as shown in figure 6, the resistance value of the resistance in the deposition area of the resistor increases along with the rise of the temperature, the TCR test shown in figure 6 has no influence on the surface of a coating, and the influence of the temperature change on the resistance in the deposition area of the resistor is known to be small, so that the embedded resistor can be manufactured, and the thermal stability of the resistor is good.
Claims (6)
1. A method for preparing a high-resistance embedded resistor by chemically doping carbon is characterized by comprising the following steps:
step 1: printed circuit patterning
Manufacturing a resistance pattern on the surface of the copper-clad plate by adopting a printed circuit manufacturing process to obtain a patterned printed circuit board;
and 2, step: sensitization/hydrolysis of stannous chloride
Soaking a patterned printed circuit board in a stannous chloride aqueous solution for sensitization, soaking the patterned printed circuit board in deionized water for hydrolysis after sensitization, and depositing a layer of stannous salt gel Sn slightly soluble in water on the surface of a substrate of the patterned printed circuit board2(OH)3Cl；
And step 3: palladium chloride activation
Sn is deposited on the surface of the base material2(OH)3Soaking the Cl patterned printed circuit board in PdCl2In aqueous solution, so that Sn2(OH)3Pd in palladium chloride solution by Cl2+Reducing ions into Pd atoms and depositing the Pd atoms on the surface of the base material of the graphical printed circuit board so as to form a chemical plating activation center;
and 4, step 4: graphics fabrication
Sticking an adhesive tape on the surface of the graphical printed circuit board processed in the step 3, and covering a region where the embedded resistor is not required to be manufactured by using a resistor graphical adhesive tape to expose a manufacturing region of the embedded resistor;
and 5: chemical plating embedded resistor
Carrying out chemical plating in the embedded resistor manufacturing area to obtain chemical plating solution with the nickel content of 52-82%, the phosphorus content of 8-29%, the carbon content of 4-11% and the oxygen content of 3.5-8%, wherein the chemical plating solution comprises the following components in concentration: 10-55g/L of nickel sulfate or nickel chloride, 10-50 g/L of sodium hypophosphite, 2-20 g/L of buffer solution, 5-40 g/L of complexing agent and 0-4 ml/L of resistance value regulator, wherein when the plating solution is prepared, the pH value is regulated to be 4.5-6.5 by adopting the pH value regulator, and the temperature is kept to be 70-90 ℃ in the using process of the plating solution;
step 6: annealing of
And (4) carrying out heat treatment on the carbon-doped nickel-phosphorus alloy embedded resistor obtained in the step (5) at the temperature of 120-200 ℃ for more than 30 minutes to obtain the embedded resistor with stable resistance.
2. The method of claim 1, wherein the method comprises the steps of: and in the step 5, the buffer solution is at least one of sodium acetate or potassium acetate.
3. The method of claim 1, wherein the method comprises the steps of: in the step 5, the complexing agent is at least one of sodium citrate, succinic acid, thiourea, DL malic acid or lactic acid and triethylamine.
4. The method of claim 1, wherein the carbon is chemically doped to form a high resistance embedded resistor, and the method comprises: in the step 5, the resistance value regulator is at least one of diethylenetriamine or beta-alanine.
5. The method of claim 1, wherein the carbon is chemically doped to form a high resistance embedded resistor, and the method comprises: and in the step 5, the pH regulator is at least one of ammonia water, sodium hydroxide, potassium hydroxide and glacial acetic acid.
6. The method of claim 1, wherein the method comprises the steps of: and 6, annealing treatment, namely putting the resistor cleaned by the deionized water into an oven to dry the surface.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210452545.0A CN114783712A (en) | 2022-04-27 | 2022-04-27 | Method for preparing high-resistance embedded resistor by chemically doping carbon |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210452545.0A CN114783712A (en) | 2022-04-27 | 2022-04-27 | Method for preparing high-resistance embedded resistor by chemically doping carbon |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102324294A (en) * | 2011-08-16 | 2012-01-18 | 电子科技大学 | Preparation method of embedded resistance material |
| CN102438404A (en) * | 2011-08-16 | 2012-05-02 | 电子科技大学 | Preparation method of embedded resistor for printed circuit board |
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2022
- 2022-04-27 CN CN202210452545.0A patent/CN114783712A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102324294A (en) * | 2011-08-16 | 2012-01-18 | 电子科技大学 | Preparation method of embedded resistance material |
| CN102438404A (en) * | 2011-08-16 | 2012-05-02 | 电子科技大学 | Preparation method of embedded resistor for printed circuit board |
Non-Patent Citations (1)
| Title |
|---|
| 罗宇兴；周国云；张伟豪等: ""印制电路高阻值NiPC电阻薄膜及其性能研究"", 《印制电路信息》 * |
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Application publication date: 20220722 |