( 12 ) United States Patent
`Liu et al .
`
`( 10 ) Patent No . : US 10 , 344 , 391 B2
`Jul . 9 , 2019
`( 45 ) Date of Patent :
`
`US010344391B2
`
`( 73 )
`
`( * ) Notice :
`
`( 54 ) FE - NI - P - RE MULTICOMPONENT ALLOY
`PLATING LAYER , AND
`ELECTRODEPOSITION PREPARATION
`METHOD AND APPLICATION THEREOF
`( 71 ) Applicant : INSTITUTE OF METAL
`RESEARCH CHINESE ACADEMY
`OF SCIENCES , Liaoning ( CN )
`( 72 ) Inventors : Zhiquan Liu , Liaoning ( CN ) ; Di Wu ,
`Liaoning ( CN ) ; Liyin Gao , Liaoning
`( CN ) ; Jingdong Guo , Liaoning ( CN )
`Assignee : INSTITUTE OF METAL
`RESEARCH , CHINESE ACADEMY
`OF SCIENCES , Liaoning ( CN )
`Subject to any disclaimer , the term of this
`patent is extended or adjusted under 35
`U . S . C . 154 ( b ) by 844 days .
`( 21 ) Appl . No . :
`14 / 784 , 177
`( 22 ) PCT Filed :
`Oct . 24 , 2013
`( 86 ) PCT No . :
`PCT / CN2013 / 085885
`§ 371 ( C ) ( 1 ) ,
`Oct . 13 , 2015
`( 2 ) Date :
`( 87 ) PCT Pub . No . : WO2015 / 054930
`PCT Pub . Date : Apr . 23 , 2015
`Prior Publication Data
`US 2016 / 0053396 A1
`Feb . 25 , 2016
`Foreign Application Priority Data
`( 30 )
`Oct . 16 , 2013 ( CN ) . . . . . . . . . . . . . . . . . . . . . . . . . . 2013 1 0489128
`( 51 )
`Int . CI .
`C250 3 / 56
`B32B 15 / 01
`
`( 65 )
`
`( 2006 . 01 )
`( 2006 . 01 )
`( Continued )
`
`( 52 ) U . S . CI .
`CPC . . . . . . . . . . . . C250 3 / 562 ( 2013 . 01 ) ; B32B 15 / 015
`( 2013 . 01 ) ; C25D 3 / 56 ( 2013 . 01 ) ; C25D 5 / 34
`( 2013 . 01 ) ; C25D 21 / 12 ( 2013 . 01 ) ; C25D
`21 / 14 ( 2013 . 01 )
`( 58 ) Field of Classification Search
`®
`CPC . . . . . . . . . . . . . . .
`. . . . . . . . . . . . . . . . C25D 3 / 562 ; C25D 3 / 56
`( Continued )
`References Cited
`U . S . PATENT DOCUMENTS
`3 , 271 , 276 A *
`9 / 1966 Di Guilio . . . . . . . . . . . . . . . . . C25D 3 / 56
`148 / 312
`5 , 013 , 411 A *
`5 / 1991 Minowa . . . . . . . . . . . . . . . . H01F 1 / 0577
`148 / 102
`2005 / 0263216 A1 * 12 / 2005 Chin . . . . . . . . . . . . . . . . . . . C22C 45 / 02
`148 / 304
`
`( 56 )
`
`CN
`CN
`
`FOREIGN PATENT DOCUMENTS
`1051060 A
`5 / 1991
`1978710 A
`6 / 2007
`( Continued )
`
`OTHER PUBLICATIONS
`Li et al . , “ Effects of Rare Earth on Composite Ni - Fe - P - RE Alloy
`Coating , " Electroplating & Pollution Control ( Jul . 2007 ) , vol . 27 ,
`No . 4 , pp . 1 - 10 . ( Year : 2007 ) . *
`( Continued )
`Primary Examiner — Edna Wong
`( 74 ) Attorney , Agent , or Firm — Smith , Gambrell &
`Russell , LLP
`ABSTRACT
`( 57 )
`An Fe - Ni - P - RE multicomponent alloy plating layer ,
`electrodeposition preparation method , and plating applica
`tion . The alloy plating layer obtained via electrodeposition
`contains elements Fe , Ni , P and RE , with the following mass
`percentages Fe
`16 % - 65 % , Ni — 25 % - 70 % , combined Fe
`and Ni - 63 % - 91 % , RE 1 . 6 % - 25 % , and the balance being
`P . The plating solution mainly contains the following com
`( Continued )
`
`R
`
`AYMAPLATIN
`
`alegos
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`US 10 , 344 , 391 B2
`Page 2
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`ponents : ferrous salt , nickel salt , NaH2PO2 , REC13 , H2B03
`and Na2C H307 . A multicomponent alloy plating layer of
`different components can be obtained by adjusting the main
`salt and complexing agent in the plating solution and by
`adjusting the process Enabled is controllable adjustment to
`the components of the obtained plating layer while saving
`costs , improved characteristics such as the thermal expan
`sion coefficient , electrical property , magnetic property , etc . ,
`and products and methods very suitable for applications in
`the field of micro - electronics .
`13 Claims , 9 Drawing Sheets
`
`101353790 A
`S6167754 A
`H01 - 180994
`H0729734 A
`
`1 / 2009
`4 / 1986
`7 / 1989
`1 / 1995
`
`OTHER PUBLICATIONS
`International Search Report for PCT / CN2013 / 085885 , dated Jul . 29 ,
`2014 in English & Chinese Language .
`Written Opinion of the International Search Authority dated Jul . 29 ,
`2014 for International Patent Application No . PCT / CN2013 / 085885
`( 5 pages in Chinese with English Translation ) .
`International Preliminary Report on Patentability dated Apr . 16 ,
`2016 for International Patent Application No . PCT / CN2013 / 085885
`( 6 pages in Chinese with English Translation ) .
`Chinese Search Report for Chinese Patent Application No .
`2013104891284 dated Feb . 29 , 2016 ( 1 page ) .
`Chinese Office Action for Chinese Patent Application No .
`2013104891284 dated Apr . 1 , 2016 ( 5 pages in Chinese with
`English Translation ) .
`Li , Jin - hui , et al . Effects of Rare Earth on Composite Ni - Fe - P - RE
`Alloy Coating . Electroplating & Pollution Control . 2007 . vol . 27 ,
`No . 4 , pp . 12 - 13 . English abstract on p . 1 .
`Weng , Sen - Lin , et al . Mechanism of Electro Deposition of Fe - Ni - P
`Alloy . Journal of Huaqiao University ( Natural Science ) . 2007 . vol .
`28 , No . 3 , pp . 275 - 277 . English abstract on p . 3 .
`
`Int . CI .
`( 2006 . 01 )
`C25D 5 / 34
`( 2006 . 01 )
`C25D 21 / 12
`C25D 21 / 14
`( 2006 . 01 )
`Field of Classification Search
`USPC
`. . . . . . . . . . . . . . . . . . . . . . . 205 / 258 , 259
`See application file for complete search history .
`References Cited
`
`( 51 )
`
`( 58 )
`
`( 56 )
`
`CN
`
`FOREIGN PATENT DOCUMENTS
`101311307
`11 / 2008
`
`* cited by examiner
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`atent
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`Jul . 9 , 2019
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`Sheet 1 of 9
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`US 10 , 344 , 391 B2
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`TEMATURE OF THE PLATING
`
`Figure 1
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`atent
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`Sheet 2 of 9
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`US 10 , 344 , 391 B2
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`Sheet 3 of 9
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`Jul . 9 , 2019
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`Sheet 4 of 9
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`US 10 , 344 , 391 B2
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`Sheet 5 of 9
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`US 10 , 344 , 391 B2
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`Sheet 6 of 9
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`US 10 , 344 , 391 B2
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`U . S . Patent
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`atent
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`Jul . 9 , 2019
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`Sheet 7 of 9
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`US 10 , 344 , 391 B2
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`Sheet 8 of 9
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`US 10 , 344 , 391 B2
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`Jul . 9 , 2019
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`Sheet 9 of 9
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`US 10 , 344 , 391 B2
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`US 10 , 344 , 391 B2
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`layer is electrically deposited on substrate at constant volt
`FE - NI - P - RE MULTICOMPONENT ALLOY
`age or constant current , wherein : the used plating solution
`PLATING LAYER , AND
`comprises main salt ( s ) , complexing agent ( s ) and water , the
`ELECTRODEPOSITION PREPARATION
`chemical composition and concentration of said main salt ( s )
`METHOD AND APPLICATION THEREOF
`5 are : ferrite being 0 . 01 - 0 . 09 mol / L , nickel salt ( s ) being 0 . 01
`0 . 09 mol / L , NaH PO , being 0 . 1 mol / L , REC1 , being 0 . 5 - 4
`TECHNICAL FIELD
`g / L , HZBO ; being 0 . 5 mol / L , said complexing agent being
`Na2C , H , O , with a concentration of 0 . 1 - 0 . 2 mol / L in the
`The present invention relates to the field of electroplating ,
`plating solution , the balance being water . HC1 or H , SO , is
`specifically to a FeNi — P - RE multicomponent alloy plat
`used to adjust the pH value of the plating solution to 2 - 5 and
`ing layer and the electrodeposition method and application 10 the the temperature of the plating solution is 45 - 70° C .
`thereof . The prepared alloy plating layer is suitable for
`The current density at constant current is 3 . 0 - 9 . 0 A / dm3
`applications in fields such as microelectronics and semicon
`and the voltage at constant voltage is - 0 . 9m - 3 . 0 V .
`ductor function devices .
`In said plating solution , the ferrite ( s ) is one or two
`selected from FeSO4 and FeCl2 . The nickel salt ( s ) is one or
`BACKGROUND OF THE INVENTION
`15 two from Niso , and Nici , . Said plating solution can also
`comprise an assistant complexing agent ( s ) to promote co
`Fe — Ni alloys represented by Invar alloy , Kovar alloy and
`deposition of multicomponent system whose concentration
`is 0 . 005 - 0 . 015 mol / L .
`perm - alloy , are widely accepted for their advantages of the
`performance in thermal expansion and soft magnetic prop -
`Said assistant complexing agent ( s ) can be one or two from
`erties . In recent years , following the development of tech - 20 EDTA - 2Na or NH _ C1 .
`nologies in the microelectronics industry , the advantages of
`Said plating solution can also comprise a brightener and
`FeNi alloy materials in nature such as lead - free solder -
`a wetting agent to improve the surface quality of plating .
`ability and interface reaction rate are gradually being rec -
`Said brightener is saccharin sodium or butynediol with a
`ognized by researchers and investigated in depth . The
`concentration of 0 . 5 - 2 . 5 g / L . Said wetting agent is sodium
`related achievements are being published continuously from
`25 dodecyl sulfate with a concentration of 0 . 1 - 0 . 5 g / L .
`the studies . A large amount of study data shows that FeNi
`According to the present invention , before electrodepo
`thin film materials hold good solder - ability and slow inter -
`sition of alloy plating layer on a substrate , a copper sheet is
`face reaction rate . It lays the foundation for the wide
`treated on the surface to remove any dust , oil or grease and
`application of Fe - Ni thin film materials in the micro -
`oxide , etc . Then 5 % H2SO4 is used to activate its surface .
`electronics industry . Nevertheless , if used as magnetic core 30 Then the substrate is washed with de - ionized water before
`of inductor devices in chips , the existing Fe - Ni thin film
`placed in
`a plating tank to carry out electrodeposition
`materials tend to consume energy in their high - frequency
`process .
`application , which results in a rapid decrease of inductance
`The ratio among different components in the plating layer
`and lost advantages in power conversion . Therefore , more
`can be adjusted through modifying the content ( s ) of the
`research is urged to carry out further studies in order to
`35 main salt ( s ) , the content ( s ) of the complexing agent ( s ) in the
`plating solution and any one or more process parameters
`improve the performance of materials .
`Compared with the preparation methods such as magne
`during the process of electrodeposition .
`tron sputtering , chemical vapor deposition ( CVD ) and atom
`The alloy plating layer according to the present invention
`layer deposition frequently used in the microelectronics
`is applied in the fields such as microelectronics and semi
`industry , the electroplating method is preferred in the indus - 40 conductor function devices .
`tries due to its advantages of low upfront investment on
`The principle of the present invention is as follows :
`equipment , easy and feasible operation , short cycle of mate
`The magnetism of solid material comes from the spin and
`rial preparation , high efficiency , low operation cost , etc .
`orbital motion of various charged particles . As for transition
`metals , the wave functions of 3d electrons overlap between
`SUMMARY OF THE INVENTION
`45 each other to provide the metals such as Fe , Co , Ni , Yb , Gd
`and their alloys ferromagnetism through direct exchange
`In view of the shortcomings of existing technologies , the
`interaction . As for rare earth metals , the 4f electron cloud of
`present invention aims to provide a Fe - Ni - P - RE multi -
`the adjacent atoms do not overlap with each other . But the
`component alloy plating layer as well as the electrodeposi -
`s itinerant electrons can function as a medium through
`tion method and application thereof .
`50 indirect exchange interaction to cause f electrons to change
`Through adding appropriate additives and adjusting the
`spin orientation and hence show spin magnetization : for
`process parameters , an alloy plating layer with controllable
`light rare earth metals whose atomic number is smaller than
`composition is obtained through electroplating .
`Gd , the magnetic moment of 3d atom is parallel with the
`In order to realize the purposes above , the technical
`magnetic moment of 4f atom , so the magnetic moments of
`55 them ferromagnetic couple with each other ; for heavy rare
`scheme of the present invention is :
`A FeNi — P - RE multicomponent alloy plating layer that
`earth metal whose atomic number is higher than Gd , the
`is plated on a substrate by means of electroplating comprises
`corresponding magnetic moments are anti - parallel showing
`the elements of Fe , Ni , P and RE , wherein the mass
`ferri - magnetic coupling effect . If the rare earth element ( s ) is
`percentages of various elements are respectively : Fe being
`added in Fe , Ni , the Slater - Pauling curve can be used to
`20 ~ 65 % , Ni being 25 ~ 70 % , Fe + Ni being 65 ~ 90 % , RE being 60 analyze the atomic magnetic moment and the magneto
`2 ~ 25 % , the balance being P ; and RE being rare earth
`crystalline anisotropy exerted by rare earth metal . Mean
`while , with the synergistic effect from the factors such as
`element .
`Said rare earth element is one or two selected from La , Ce ,
`crystallite size , structure and material internal stress , the
`magnetism of material can also be controllable . The present
`Pr , Nd , Eu , Gd and Tb .
`Said substrate is copper or other metal material .
`65 invention adds an appropriate amount of rare earth
`An electrodeposition preparation method of said Fe -
`element ( s ) in the FeNi ( P ) alloy to realize a controllable
`Ni — P - RE multicomponent alloy plating layer that the alloy
`management
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`US 10 , 344 , 391 B2
`
`15
`
`FIG . 13 is the composition analytical curve of the sample
`on the magnetic performances of material such as coercivity ,
`plating layer of example 6 .
`magnetization intensity and magnetic anisotropy . Through
`FIG . 14 is the magnetic performance curve of the sample
`adding P element in the plating solution , the electrical
`plating layer of example 6 .
`property of the plating layer is improved and hence the
`FIG . 15 is the X - Ray diffraction spectrum of the sample
`energy loss at high frequency can be decreased . Through 5
`plating layer of example 7 .
`adding rare earth element ( s ) , the performances are improved
`FIG . 16 is the morphology picture of the sample plating
`in terms of the stability of plating solution , the magnetic
`layer of example 7 .
`performance of plating layer and the corrosion resistance .
`The method according to the present invention can produce
`FIG . 17 is the composition analytical curve of the sample
`a multicomponent alloy plating layer with different compo - 10 plat
`" U plating layer of example 7 .
`sitions through adjusting the formula of plating solution and
`FIG . 18 is the performance curve of the sample plating
`the parameters of plating process . Hence , the material indi
`layer of example 7 .
`ces such as thermo expansion coefficient , resistivity , and
`saturation magnetic induction can be further regulated to
`DETAILED DESCRIPTION OF THE
`expand the application of Fe - Ni alloy materials .
`PREFERRED EMBODIMENTS
`The present invention has the following advantages :
`1 . The present invention can produce a Fe — Ni — P - RE
`The process flow chart of the present invention is as
`multicomponent alloy plating layer . Through adjusting the
`11
`shown in FIG . 1 and specified as follows :
`content ( s ) of the main salt ( s ) and the content ( s ) of the
`The plating solution according to the present comprises
`he 20
`complexing agent ( s ) in the plating solution as well as the 20
`main salt ( s ) , complexing agent ( s ) and water .
`process parameters during electrodeposition , the alloy plat
`The chemical composition and concentration of said main
`ing layer can be produced to have different compositions so
`salt ( s ) are : ferrite of 0 . 01 - 0 . 09 mol / L , nickel salt ( s ) of
`as to expand the application of materials .
`0 . 01 - 0 . 09 mol / L . NaH , PO , of 0 . 1 mol / L , RECl2 of 0 . 5 - 4
`2 . In the FeNi - P - RE multicomponent alloy plating
`layer prepared according to the present invention , the mass 25 g / L , HZBOZ of 0 . 5 mol / L ; said complexing agent is
`percentage of Fe in the plating solution is 20 % - 65 % , 25 % -
`Na2C6H30 , of a concentration of 0 . 1 - 0 . 2 mol / L in the
`70 % for Ni , 65 % - 90 % for sum of Fe and Ni . The ratio
`plating solution , the balance being water . HCl or H2SO4 is
`between Fe , Ni and rare earth component can be adjusted to
`used to adjust the pH value of the plating solution to 2 ~ 5 ,
`realize the modification on thermal expansion coefficient ,
`and the temperature of the plating solution is 45 - 70° C .
`magnetic property , and electrical property of film material . 30
`On the basis of the basic composition as above , the plating
`3 . The FeNi — P - RE plating layer prepared according to
`solution according to the present invention can also further
`the present invention has an improved of electric property
`comprise assistant complexing agent ( s ) ( EDTA - 2Na and / or
`through adding P element in the plating solution to reduce
`NH C1 ) to promote co - deposition of multicomponent sys
`the energy loss at high - frequency application . Through
`tem . Brightener ( including but not limit to saccharin sodium ,
`adding rare earth element , the magnetic property of plating 35 butynediol ) and wetting agent ( sodium dodecyl sulfate ) , etc . ,
`layer is improved . Meanwhile , the surface quality is also
`can also be added to improve the surface quality of the
`plating layer .
`improved without adding any additive .
`4 . The plating solution system used in the present inven -
`The formulating method according to the present inven
`tion is simple , stable , low in concentration of various
`tion is : adding HZBO2 into appropriate amount of de - ionized
`components , easy to extend the application and economi - 40 water to dissolve completely , then adding Na2CH 07 . 2H2O
`into the solution with agitating , and then adding the raw
`cally beneficial in saving cost .
`materials of the main salts such
`as FeSO4 . 7H2O ,
`BRIEF DESCRIPTION OF THE DRAWINGS
`NiSO4 . 6H20 , NaH2PO2 . H2O and REC1z . nH2O in turn with
`agitating to mix evenly , if necessary , adding the solutions of
`FIG . 1 is the process flow chart .
`45 a brightener , wetting agent and so forth , at last adding the
`de - ionized water to the specified volume .
`FIG . 2 is the morphology picture of the sample plating
`layer of example 1 .
`The electrodeposition process according to the present
`FIG . 3 is the X - Ray diffraction spectrum of the sample
`invention is : adjusting the pH value of the plating solution
`plating layer of example 1 .
`to 2 - 5 with HCl or H , SO2 , then heating to 45 - 70° C . ;
`FIG . 4 is the composition analytical curve of the sample 50 meanwhile , treating the surface of substrate ( copper sheet or
`plating layer of example 1 .
`other metal material ) to remove any dust , oil or grease ,
`FIG . 5 is the morphology picture of the sample plating
`oxide , etc . Specifically , using 5 wt . % diluted solution of
`layer of example 2 .
`H , SO , to activate the surface and washing away the de
`FIG . 6 is the composition analytical curve of the sample
`ionized water before placing it in the plating tank ; carrying
`plating layer of example 2 .
`55 out the electrodeposition process at constant voltage or
`FIG . 7 is the morphology picture of the sample plating
`constant current .
`layer of example 3 .
`FIG . 8 is the composition analytical curve of the sample
`plating layer of example 3 .
`FIG . 9 is the X - Ray diffraction spectrum of the sample 60
`plating layer of example 4 .
`FIG . 10 is the composition analytical curve of the sample
`plating layer of example 4 .
`FIG . 11 is the X - Ray diffraction spectrum of the sample
`plating layer of example 6 .
`FIG . 12 is the morphology picture of the sample plating
`layer of example 6 .
`
`EXAMPLE 1
`Treat the surface of copper sheet substrate : remove any
`dust , oil or grease , oxide ; use 5 % diluted solution of H2SO4
`to activate the surface and wash it with the de - ionized water
`before placing it in the plating tank . The composition of the
`plating solution is : FeSO4 of 0 . 039 mol / L , NISO4 of 0 . 061
`65 mol / L , NaH2PO2 of 0 . 1 mol / L , CeCl2 of 1 g / L , H2B02 of 0 . 5
`mol / L , Na2C6H30 , of 0 . 1 mol / L , the balance being water .
`Adjust the pH value of the plating solution to 2 and heat it
`
`Ex.1020 / IPR2022-00117 / Page 13 of 15
`APPLE INC. v. SCRAMOGE TECHNOLOGY, LTD.
`
`

`

`US 10 , 344 , 391 B2
`
`10
`
`plating layer is as shown in FIG . 10 and the composition of
`to 57° C . Then select a constant voltage of - 1 . 05V and an
`the prepared plating layer is : 48 . 77Fe 39 . 26Ni 10 . 16P1 . 80La
`electroplating duration of 5 min to carry out the electrode -
`position process .
`( mass percentage ) .
`The thickness of the sample copper substrate is 250 um ,
`The surface morphology of the plating layer is as shown
`in FIG . 2 . The X - Ray diffraction spectrum of the plating 5 the thickness of the plating layer is 4 . 29 um , the surface
`layer is as shown in FIG . 3 . The composition analytical
`resistance of the plating layer is measured as 9 . 32 * 10 - 2
`curve of the plating layer is as shown in FIG . 4 and the
`and the total magnetic moment in the direction parallel to the
`composition of the prepared plating layer is : 54 . 25Fe
`plating layer is 98 . 92 memu .
`34 . 87Ni 9 . 25P1 . 63Ce ( mass percentage ) .
`EXAMPLE 5
`EXAMPLE 2
`Treat the surface of copper sheet substrate : remove any
`Treat the surface of copper sheet substrate : remove any
`dust , oil or grease , oxide ; use 5 % diluted solution of H2SO4
`to activate the surface and wash it with the de - ionized water
`dust , oil or grease , oxide ; use 5 % diluted solution of H , SO
`to activate the surface and wash it with the de - ionized water 15 before placing it in the plating tank . The composition of the
`before placing it in the plating tank . The composition of the
`plating solution is : FeSO4 of 0 . 020 mol / L . NISO , of 0 . 080
`plating solution is : FeSO4 of 0 . 020 mol / L , NISO , of 0 . 080
`mol / L , NaH , PO , of 0 . 15 mol / L , CeCl , of 1 g / L , H , BO , of
`mol / L , NaH2PO2 of 0 . 1 mol / L , CeCl2 of 1 g / L , HZBO2 of 0 . 5
`0 . 5 mol / L , NazC6H30 , of 0 . 1 mol / L , the balance being
`mol / L , Na2C , H , O , of 0 . 1 mol / L , the balance being water .
`water . Adjust the pH value of the plating solution to 2 and
`Adjust the pH value of the plating solution to 2 and heat it 20 heat it to 55° C . Then select a constant voltage of - 1 . 05V
`to 55° C . Then select a constant voltage of - 1 . 20V and an
`and an electroplating duration of 30 min to carry out the
`electroplating duration of 10 min to carry out the electrode
`electrodeposition process .
`The composition of the prepared plating layer is : 27 . 97Fe
`position process .
`The surface morphology of the plating layer is as shown
`35 . 73Ni 13 . 56P22 . 74Ce ( mass percentage ) .
`The thickness of the sample copper substrate is 250 um ,
`in FIG . 5 . The composition analytical curve of the plating 25
`layer is as shown in FIG . 6 and the composition of the
`the thickness of the plating layer is 2 . 11 um , the surface
`prepared plating layer is : 38 . 27Fe 46 . 8Ni 12 . 4P2 . 54Ce
`resistance of the plating layer is measured as 2 . 33 * 10 - 2
`and the total magnetic moment in the direction parallel to the
`( mass percentage ) .
`The thickness of the copper substrate is 250 um , the
`plating layer is 19 . 85 memu .
`thickness of the plating layer is 2 . 39 um and the total 30
`EXAMPLE 6
`magnetic moment in the direction parallel to the plating
`layer is 23 . 90 memu .
`Carry out sputter deposition of 100 nm of Ti layer and 400
`nm of Cu layer on a wafer and then dice it to appropriate
`EXAMPLE 3
`35 size ; treat the surface of the sample : remove any dust , oil or
`Treat the surface of copper sheet substrate : remove any
`grease , oxide ; use 5 % diluted solution of H SO , to activate
`dust , oil or grease , oxide ; use 5 % diluted solution of H2SO4
`the surface and wash it with the de - ionized water before
`to activate the surface and wash it with the de - ionized water
`placing it in the plating tank . The composition of the plating
`before placing it in the plating tank . The composition of the
`solution is : FeSO4 of 0 . 039 mol / L , NISO4 of 0 . 061 mol / L ,
`plating solution is : FeSO , of 0 . 010 mol / L , NISO , of 0 . 090 40 NaH , PO , of 0 . 1 mol / L , CeCl2 of 1 g / L , H , BO2 of 0 . 5 mol / L ,
`mol / L , NaH2PO2 of 0 . 1 mol / L , CeCl2 of 1 g / L , H2B02 of 0 . 5
`Na2C6H30 , of 0 . 1 mol / L , the balance being water . Adjust
`mol / L , Na2C6H30 , of 0 . 1 mol / L , the balance being water .
`the pH value of the plating solution to 2 and heat it to 55°
`Adjust the pH value of the plating solution to 2 and heat it
`C . Then select a constant voltage of 0 . 36 A and an electro
`to 55° C . Then select a constant voltage of - 1 . 05V and an
`plating duration of 30 min to carry out the electrodeposition
`electroplating duration of 10 min to carry out the electrode - 45 process .
`position process .
`The X - Ray diffraction spectrum of the plating layer is as
`The surface morphology of the plating layer is as shown
`shown in FIG . 11 . The surface morphology of the plating
`in FIG . 7 . The composition analytical curve of the plating
`layer is as shown in FIG . 12 . The composition analytical
`layer is as shown in FIG . 8 and the composition of the
`curve of the plating layer is as shown in FIG . 13 and the
`prepared plating layer is : 16 . 83Fe 65 . 54Ni 11 . 56P6 . 07Ce 50 composition of the prepared plating layer is : 58 . 18Fe
`31 . 72Ni 6 . 13P3 . 97Ce ( mass percentage ) . The thickness of
`( mass percentage ) .
`the plating layer is 19 . 9 um and the resistivity of the plating
`EXAMPLE 4
`layer is measured as 3 . 45 22 . um . The hysteresis loop of the
`plating layer is as shown in FIG . 14 . The coercivity in the
`Treat the surface of copper sheet substrate : remove any 55 direction parallel to the plating layer is 4 . 99 Oe and the
`dust , oil or grease , oxide ; use 5 % diluted solution of H2SO4 magnetization intensity is 677 . 99 emu / cm " . The coercivity
`to activate the surface and wash it with the de - ionized water
`in the direction perpendicular to the plating layer is 28 . 46 Oe
`before placing it in the plating tank . The composition of the
`and the magnetization intensity is 677 . 99 emu / cm " .
`plating solution is : FeSO4 of 0 . 039 mol / L , NISO2 of 0 . 061
`mol / L , NaH , PO , of 0 . 1 mol / L , LaCl2 of 1 g / L , H , BO2 of 0 . 5 60
`EXAMPLE 7
`mol / L , Na2CH , 0 , of 0 . 1 mol / L , the balance being water .
`Adjust the pH value of the plating solution to 2 and heat it
`Carry out sputter deposition of 100 nm of Ti layer and 400
`to 55° C . Then select a constant voltage of - 1 . 2V and an
`nm of Cu layer on a wafer and then dice it to appropriate
`electroplating duration of 5 min to carry out the electrode -
`size ; treat the surface of the sample : remove any dust , oil or
`position process .
`65 grease , oxide ; use 5 % diluted solution of H2SO4 to activate
`The X - Ray diffraction spectrum of the plating layer is as
`the surface and wash it with the de - ionized water before
`placing it in the plating tank . The composition of the plating
`shown in FIG . 9 . The composition analytical curve of the
`
`Ex.1020 / IPR2022-00117 / Page 14 of 15
`APPLE INC. v. SCRAMOGE TECHNOLOGY, LTD.
`
`

`

`US 10 , 344 , 391 B2
`
`solution is : FeSO4 of 0 . 03 mol / L , NISO4 of 0 . 07 mol / L ,
`one or two selected from FeSO4 and FeCl2 ; the nickel salt or
`NaH2PO2 of 0 . 1 mol / L , LaCl2 of 1 g / L , H2B02 of 0 . 5 mol / L ,
`salts is one or two selected from NiSO4 and Niclz .
`Na2C6H , 0 , of 0 . 1 mol / L , the balance being water . Adjust
`5 . The electrodeposition method of the Fe - Ni - P - RE
`the pH value of the plating solution to 2 and heat it to 55°
`multicomponent alloy plating layer according to claim
`1 ,
`C . Then select a constant voltage of 0 . 36 A and an electro -
`5 wherein said one or more complexing agents further com
`plating duration of 30 min to carry out the electrodeposition
`prises , in a concentration of 0 . 005 - 0 . 015 mol / L , one or two
`process .
`selected from EDTA - 2Na and NH _ C1 .
`The X - Ray diffraction spectrum of the plating layer is as
`6 . The electrodeposition method of the Fe — Ni - P - RE
`shown in FIG . 15 . The surface morphology of the plating
`multicomponent alloy plating layer according to claim 1 ,
`layer is as shown in FIG . 16 . The composition analytical 10 wherein said plating solution further comprises a brightener
`curve of the plating layer is as shown in FIG . 17 and the
`that is saccharin sodium or butynediol , and the concentration
`composition of the prepared plating layer is : 54 . 84Fe
`of said brightener is 0 . 5 - 2 . 5 g / L ; and a wetting agent that is
`35 . 91Ni 5 . 14P4 . 11La ( mass percentage ) . The thickness of
`sodium dodecyl sulfate of a concentration of 0 . 1 - 0 . 5 g / L .
`the plating layer is 18 . 3 um and the resistivity of the plating
`7 . The electrodeposition method of the Fe - Ni - P - RE
`layer is measured as 6 . 92 2 . um . The hysteresis loop of the 15
`multicomponent alloy plating layer according to claim 1 ,
`plating layer is as shown in FIG . 18 . The coercivity in the
`further comprising treating a surface of the substrate as
`direction parallel to the plating layer is 20 . 39 Oe and the
`follows : activating the surface with 5 wt . % of diluted
`magnetization intensity is 413 . 72 emu / cmº . The coercivity
`in the direction perpendicular to the plating layer is 38 . 55 Oe H2SO4 , and then washing the surface with de - ionized water
`a plating tank to carry out the
`200 and placing the surface in
`and the magnetization intensity is 381 . 38 emu / cmº .
`electrodeposition method .
`The examples described as above are the preferred imple
`8 . The electrodeposition method of the Fe - Ni - P - RE
`mentations according to the present invention . Nevertheless ,
`multicomponent alloy plating layer according to claim 1