(12) United States Patent
`Mansky et al.
`
`USOO666823OB2
`US 6,668,230 B2
`Dec. 23, 2003
`
`(10) Patent No.:
`(45) Date of Patent:
`
`(54)
`
`(75)
`
`(73)
`
`(*)
`
`(21)
`(22)
`(65)
`
`(63)
`
`(51)
`(52)
`
`(58)
`
`COMPUTER READABLE MEDIUM FOR
`PERFORMING SENSOR ARRAY BASED
`MATERIALS CHARACTERIZATION
`
`Inventors: Paul Mansky, San Francisco, CA (US);
`James Bennett, Santa Clara, CA (US)
`Assignee: Symyx Technologies, Inc., Santa Clara,
`CA (US)
`Subject to any disclaimer, the term of this
`patent is extended or adjusted under 35
`U.S.C. 154(b) by 0 days.
`
`Notice:
`
`Appl. No.: 10/315,519
`Filed:
`Dec. 10, 2002
`Prior Publication Data
`US 2003/0101006 A1 May 29, 2003
`Related U.S. Application Data
`
`Continuation of application No. 09/458,398, filed on Dec.
`10, 1999, now Pat. No. 6,535,824, which is a continuation
`in-part of application No. 09/210,086, filed on Dec. 11,
`1998, now Pat. No. 6,438,497, and a continuation-in-part of
`application No. 09/210,428, filed on Dec. 11, 1998, now Pat.
`No. 6,477,479, and a continuation-in-part of application No.
`09/210,485, filed on Dec. 11, 1998.
`Int. Cl. ................................................ G01N 31100
`U.S. Cl. ........................... 702/30, 702/22; 702/104;
`702/130; 422/68. 1; 422/98; 422/82.01;
`73/863.01; 73/863.21; 700/266; 700/268;
`700/299; 204/400; 204/407
`Field of Search ............................... 702/22–24, 27,
`702/30-36, 56, 57, 65, 99, 115-116, 119,
`130, 132, 136, 183, 189: 422/82.12, 99,
`108, 82.02; 374/49, 50, 56; 73/863, 863.01,
`863.03, 863.11, 863.12; 204/400, 401, 416,
`406-410; 700/266, 268, 269,299, 300;
`435/DIG. 1, DIG. 22; 436/43, 55, 148,
`149; 205/335, 770
`
`(56)
`
`References Cited
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`U.S. PATENT DOCUMENTS
`
`(List continued on next page.)
`FOREIGN PATENT DOCUMENTS
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`DE
`
`198 OS 719
`12/1998
`(List continued on next page.)
`OTHER PUBLICATIONS
`Hasanuzzaman et al., Process Compilation of Thing Film
`Microdevices 1996, IEEE, Vol:0070, pp. 745-764.*
`(List continued on next page.)
`Primary Examiner Marc S. Hoff
`ASSistant Examiner Elias Desta
`(74) Attorney, Agent, or Firm-Dobrusin & Thennisch PC
`(57)
`ABSTRACT
`A modular materials characterization apparatus includes a
`Sensor array disposed on a Substrate, with a Standardized
`array and contact pad format; electronic test and measure
`ment apparatus for Sending electrical Signals to and receiv
`ing electrical Signals from the Sensor array; an apparatus for
`making electrical contact to the Sensors in the Standardized
`array format; an apparatus for routing Signals between one
`or more Selected Sensors and the electronic test and mea
`Surement apparatus and a computer including a computer
`readable having a computer program recorded therein for
`controlling the operator of the apparatus. The Sensor array is
`preferably arranged in a Standardized format used in com
`binatorial chemistry applications for rapid deposition of
`Sample materials on the Sensor array. The interconnection
`apparatus and Sensor array and contact pad allow measure
`ment of many different material properties by using Sub
`Strates carrying different Sensor types, with only minor
`modifications if any to the electronic test and measurement
`apparatus and test procedures. By using a Sensor array that
`is separate from the electronic apparatus, and by including
`Standardized contacting and Signal routing apparatuses, the
`apparatus creates a modular “plug-and-play System that
`eliminates the need for multiple materials characterization
`machines, and eliminates the need for application-specific
`active circuitry within the Sensor arrays themselves. Further,
`the modular Sensor array System can characterize large
`numbers of material Samples rapidly, on the order of at least
`50 Samples per hour, reducing the time needed for Screening
`of materials libraries.
`
`3.266,307 A 8/1966 DeWinter .................... 73/190
`
`39 Claims, 32 Drawing Sheets
`
`
`
`Ex.1023
`CISCO SYSTEMS, INC. / Page 1 of 71
`
`

`

`US 6,668,230 B2
`Page 2
`
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`
`* cited by examiner
`
`Ex.1023
`CISCO SYSTEMS, INC. / Page 4 of 71
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`

`

`U.S. Patent
`
`Dec. 23, 2003
`
`Sheet 1 of 32
`
`US 6,668,230 B2
`
`Deposition of
`multiple samples
`
`Electronic cles and
`measurement
`One Ormore channels
`
`Fig 9 A
`
`Electronicles
`and measurement
`equipment
`
`Deposition of
`multiple samples
`
`
`
`
`
`
`
`SensOranay
`
`Z-axis Connectors
`
`Circuit boards
`
`Multiwire cables
`and Connectors
`
`
`
`
`
`test
`and measurement
`equipment
`
`Flig- 1B
`
`Deposition of
`multiple samples
`
`
`
`
`
`SensOranay
`
`Circuitboard with on-board
`signal selection andlor routing,
`andon-board electronic test
`and measurement circuitry
`
`
`
`
`
`IFg - 1 D
`
`
`
`Deposition of
`multiple samples
`
`Substrate containing sensor array,
`signalselection and/or routing,
`and electronic testand
`measurement circuitry
`
`
`
`Fig 1E
`
`Ex.1023
`CISCO SYSTEMS, INC. / Page 5 of 71
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`

`

`U.S. Patent
`
`Dec. 23, 2003
`
`Sheet 2 of 32
`
`US 6,668,230 B2
`
`
`
`
`
`
`
`
`
`
`
`
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`Ex.1023
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`Dec. 23, 2003
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`Sheet 3 of 32
`
`US 6,668,230 B2
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`O BH BLOO BH BLOO
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`Ex.1023
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`U.S. Patent
`
`Dec. 23, 2003
`
`Sheet 4 of 32
`
`US 6,668,230 B2
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`
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`
`2
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`5
`6
`7
`8
`
`Ex.1023
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`U.S. Patent
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`Dec. 23, 2003
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`Sheet 5 of 32
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`US 6,668,230 B2
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`
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`U.S. Patent
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`Dec. 23, 2003
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`Sheet 6 of 32
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`US 6,668,230 B2
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`Ex.1023
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`U.S. Patent
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`Dec. 23, 2003
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`Sheet 7 of 32
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`US 6,668,230 B2
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`52
`
`-50
`
`126
`(OUTPUT)
`
`CIHL)
`
`
`
`
`
`
`
`Healer drive,
`Thermometer
`readout
`
`
`
`8wires per sensor
`
`
`
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`Dec. 23, 2003
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`Sheet 8 of 32
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`US 6,668,230 B2
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`
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`U.S. Patent
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`Dec. 23, 2003
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`Sheet 9 of 32
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`US 6,668,230 B2
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`
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`U.S. Patent
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`Dec. 23, 2003
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`Sheet 10 of 32
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`US 6,668,230 B2
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`/
`- - -/-
`
`-
`
`30
`
`28
`
`26
`
`24
`
`18
`
`f6
`
`14
`
`12
`
`10
`
`O
`
`50
`
`150
`
`200
`
`100
`T(C)
`
`Fig 1 1A
`
`Fig. 1 1B
`
`
`
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`Ryyas SA
`yyyyyyyyyy
`v.
`
`30
`
`40
`
`50
`
`60
`
`70
`
`80
`
`90
`
`100
`
`f0
`
`120
`
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`Dec. 23, 2003
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`Sheet 11 of 32
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`US 6,668,230 B2
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`IF 9 1 1 C g
`
`S
`
`
`
`as
`
`S
`S2
`
`O
`
`100
`
`200
`
`400
`
`500
`
`600
`
`300
`T("C)
`
`(c)
`Aluminum
`(literaturemelling point=660c
`
`0
`
`200
`
`400
`T(C)
`
`600
`
`800
`
`15
`
`10
`
`Š
`
`SE
`
`0
`
`0
`
`40
`
`A3Mg2
`(Literaturemeling point = 450c)
`
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`
`400
`T(C)
`
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`
`800
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`20
`
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`
`lead
`(literature melting point = 327c)
`200
`400
`T("C)
`
`600
`
`800
`
`p
`
`Fig 1 1D
`
`Fig 11E
`
`Fig-1 1 F
`
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`U.S. Patent
`
`Dec. 23, 2003
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`Sheet 12 of 32
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`US 6,668,230 B2
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`MODULATION FREQUENCY = 10-1000Hz
`
`0
`
`5
`
`15
`10
`SECONDS
`
`20
`
`20
`
`2o
`
`40
`
`60
`
`80
`
`to
`
`120
`
`do
`
`124
`
`
`
`
`
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`U.S. Patent
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`Dec. 23, 2003
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`Sheet 13 of 32
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`US 6,668,230 B2
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`127
`
`Programmable Voltage source to
`drive heater-ramp + modulation
`(AC+DC)
`
`Feedback/
`
`102
`ITH
`
`04
`
`102
`
`(Differential
`isloated)
`
`124
`
`
`
`approx.
`100 SensOrs
`
`126
`
`Fig 12D
`
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`Dec. 23, 2003
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`Sheet 14 of 32
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`US 6,668,230 B2
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`IF
`
`up 2 E.
`s
`
`1,50
`1.25
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`0.75
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`IF
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`
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`
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`10
`TIME (SECONDS)
`
`20
`
`25
`
`50
`
`100
`TEMP, CENTIGRADE
`
`150
`
`Ex.1023
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`Dec. 23, 2003
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`Sheet 15 of 32
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`US 6,668,230 B2
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`f
`
`10
`
`100
`
`1000
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`2000
`
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`
`100
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`10
`Hz
`Fig 12
`
`10000
`
`1000
`
`0.
`
`0.01
`1000
`
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`Dec. 23, 2003
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`Sheet 16 of 32
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`US 6,668,230 B2
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`builer
`amplifier
`
`V() (lamp)
`
`ACCurrent
`P
`O)
`sin(09
`
`LOCkin at
`frequency ()
`130
`
`DC Heatre? thermometer
`AC heater
`
`Fig - 13A
`
`L0ck in at
`frequency 3C)
`
`Programmable Voltage
`SOUrce to drive heater
`linear temperature ramp
`
`f04
`
`102
`
`126
`
`
`
`
`
`Feedback
`temp. Cont
`
`
`
`
`
`
`
`Heater Voltage, Current
`(quasi DC->gives
`Temperature
`
`-- 104
`
`130, 132
`
`-- 102
`
`-10ckin at 3CD gives
`Heat Capacity
`-lockin at CD gives
`Temperature
`
`Approx.
`100SenSOIS
`
`128
`
`Fig - 13B
`
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`O234 O
`
`0.15
`
`0.1
`
`0005OH
`0.0.
`
`O
`
`Dec. 23, 2003
`
`Sheet 17 of 32
`
`US 6,668,230 B2
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`5
`
`10
`
`15
`20
`Fig 13C
`
`25
`
`30
`
`35
`
`1
`
`N
`
`5
`
`10
`
`15
`
`20
`
`25
`
`30
`
`35
`
`Fig. 13D
`
`-5
`60x10
`
`5.5cio
`solo
`
`30
`
`-5
`
`0
`
`5
`
`25
`
`30
`
`35
`
`10
`20
`15
`time, seconds
`Fig. 13E
`
`0
`
`O
`
`100
`
`200
`
`T
`9
`
`500
`
`600
`
`400
`300
`temperature, Centgrade
`Fig. 1 3f
`
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`Sheet 18 of 32
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`US 6,668,230 B2
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`()=l ():sin(o)
`
`V
`
`V(c).2c)3CO)
`
`
`
`102
`
`104
`
`102
`
`Fig. 1 3G
`
`t
`Tg
`
`10000
`
`7500
`
`500c
`
`2500
`
`se
`
`O
`
`O
`
`100
`
`400
`
`500
`
`300
`
`200
`T(0C)
`Fig 14
`
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`Dec. 23, 2003
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`Sheet 19 of 32
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`US 6,668,230 B2
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`RTD/4pt.
`Resistance
`temperature of
`each sample
`
`
`
`SeSOIS
`RAPID
`SCAN
`
`Single-point measurement/
`control of block
`temperature
`
`Fig 15A
`
`126
`
`Computer
`
`Fig - 15B
`
`154
`
`100
`SeSOS
`
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`Dec. 23, 2003
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`Sheet 20 of 32
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`US 6,668,230 B2
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`- Temperature/exOthem
`-Dielectric spectorScopy
`(' E.)
`(, .)
`(, .)
`SeSO
`"N-Q-4 G. G.
`160
`
`Glass
`
`
`
`v TT ruly 1.
`
`Fig 1.6A
`
`Dielectric measurements Of
`5-minute epoxy Curing
`
`-O- A B mixed
`
`
`
`225
`
`S
`
`200
`
`1.75
`
`150
`
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`U.S. Patent
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`Dec. 23, 2003
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`Sheet 21 of 32
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`
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`Dec. 23, 2003
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`Sheet 22 of 32
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`US 6,668,230 B2
`
`impedence
`analyzer
`
`to, from
`SeSOS -
`rapid
`
`
`
`Single-point measurement
`Control of block
`temperature
`
`
`
`Fig.16E
`
`o
`
`C
`
`66
`
`R
`
`160
`
`SeSOS
`
`170 -
`
`
`
`176
`
`Fig 17A
`
`
`
`172
`
`- 172
`
`76
`
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`Dec. 23, 2003
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`Sheet 23 of 32
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`US 6,668,230 B2
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`
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`Dec. 23, 2003
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`Sheet 24 of 32
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`US 6,668,230 B2
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`
`
`|
`
`|| || || ||
`
`||
`
`|| ||
`
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`Dec. 23, 2003
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`Sheet 25 0f 32
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`US 6,668,230 B2
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`Sheet 26 of 32
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`US 6,668,230 B2
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`Dec. 23, 2003
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`Sheet 27 of 32
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`US 6,668,230 B2
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`
`
`OWNOISESRS580
`DIFFERENTIAL PREAMPLIFIER
`G-104f&A kHz
`
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`Dec. 23, 2003
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`Sheet 28 of 32
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`US 6,668,230 B2
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`
`
`40
`
`20
`
`O
`
`-4 O
`
`-60
`
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`Dec. 23, 2003
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`Sheet 29 of 32
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`US 6,668,230 B2
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`40
`
`20
`
`
`
`
`
`
`
`-4
`
`-8 0
`
`-100
`
`-120
`
`0
`
`20
`
`O
`
`60
`
`80
`
`
`
`
`
`100
`
`
`
`. .
`
`ONEISECKE & SCHNEIDER, 1971
`
`.
`
`ATOMIC ASB
`Fig.25
`
`V(1 kHz)
`
`
`
`=WIR Series
`
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`Dec. 23, 2003
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`Sheet 30 of 32
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`US 6,668,230 B2
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`
`
`SFE
`
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`Dec. 23, 2003
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`Sheet 31 of 32
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`US 6,668,230 B2
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`0.35
`
`15
`
`0.05
`
`150 nm A
`A 250 nm A
`
`O
`0.000
`
`0.002
`
`0.006
`
`0.008
`
`0.004
`CURRENT(AMPERES)
`Fig.27B
`
`
`
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`Dec. 23, 2003
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`Sheet 32 of 32
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`US 6,668,230 B2
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`3,0E-03
`
`20E-03
`
`S.
`S
`S
`1.OE-03
`
`0.0E+00
`48
`
`50
`
`
`
`54
`52
`RESISTANCE(OHMS)
`Fig.27D
`
`56
`
`58
`
`AIFILM THICKNESS (nm)
`Fig-28
`
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`US 6,668,230 B2
`
`1
`COMPUTER READABLE MEDIUM FOR
`PERFORMING SENSOR ARRAY BASED
`MATERIALS CHARACTERIZATION
`
`This application is a continuation of application Ser. No.
`09/458,398 filed Dec. 10, 1999 now U.S. Pat. No. 6,535,824
`which is a continuation-in-part of the following applications:
`application Ser. No. 09/210,086 filed on Dec. 11, 1998,
`which issued Aug. 20, 2002 as U.S. Pat. No. 6,438,497;
`application Ser. No. 09/210,428 filed on Dec. 11, 1998,
`which issued Nov. 5, 2002 as U.S. Pat. No. 6,477,479; and
`application Ser. No. 09/210,485 filed on Dec. 11, 1998; and
`the present application claims the benefit of the filing date of
`all these applications.
`
`RELATED CASES
`The present application is a continuation-in-part of
`co-pending U.S. patent application Ser. Nos. 09/210,086;
`09/210,428 and 09/210,485, all filed on Dec. 11, 1998, and
`are incorporated herein by reference. The present applica
`tion is also related to a PCT application (Ser. No. PCT/
`US99/3008) having the same title and filed concurrently
`herewith on Dec. 10, 1999.
`
`TECHNICAL FIELD
`The present invention is directed to a computer controlled
`apparatus for characterizing a plurality of organic or inor
`ganic materials, and more particularly to a characterization
`apparatus that uses an electrically-driven Sensor array to
`characterize a plurality of materials simultaneously and
`rapidly.
`
`5
`
`15
`
`25
`
`2
`devices measure only one material Sample at a time, Severely
`limiting the number of Samples that can be characterized per
`unit time.
`Optical Screening methods and devices have been pre
`ferred for many combinatorial chemistry and combinatorial
`materials Science applications because they are non-contact
`and non-destructive. See for example WO 98/15805, incor
`porated herein by reference. For example, luminescence
`may be Screened optically. When monitoring chemical
`reactions, for example, thermal imaging with an infrared
`camera can detect heat released during relatively fast eXo
`thermic reactions. See WO98/15813, incorporated herein by
`reference. Although optical methods are particularly useful
`for characterizing materials or properties in certain
`circumstances, many materials characterization techniques
`are difficult or impossible to perform using optical methods.
`Therefore, there is still a need for a more direct materials
`characterization method that involves more intimate contact
`between the material Samples and the Sensing apparatus.
`Conventional Sensors that generate electrical data corre
`sponding to material properties are typically designed as
`individual, discrete units, each Sensor having its own pack
`aging and wiring connections. Many materials characteriza
`tion Sensors are designed to be used individually in or with
`a machine that characterizes one Sample at a time. Linking
`a plurality of these individual Sensors in an array format,
`assuming that it is physically possible, would be expensive
`and often creates overly complicated wiring Schemes with
`minimal gains in operating efficiency for the overall Sensing
`System.
`One Structure using multiple material Samples is a micro
`fabricated array containing "microhotplates'. The microhot
`plates act as miniature heating plates for Supporting and
`Selectively heating material Samples placed thereon. U.S.
`Pat. No. 5,356,756 to Cavicchi et al and U.S. Pat. No.
`5,345,213 to Semancik et al. as well the article entitled
`“Kinetically Controlled Chemical Sensing Using Microma
`chined Structures,” by Semancik and Cavicchi, (Accounts of
`Chemical Research, Vol. 31, No. 5, 1998), all illustrate the
`microhotplate concept and are incorporated herein by ref
`erence. Although arrays containing microhotplates are
`known, they have been used primarily to create varied
`processing conditions for preparing materials. A need Still
`exists for an array-based Sensor System that can actually
`characterize material properties.
`It is therefore an object of the invention to provide a
`materials characterization System that can measure proper
`ties of many material Samples quickly, and in Some embodi
`ments Simultaneously.
`It is also an object of the invention to construct a materials
`characterization System having a modular structure that can
`be connected to a flexible electronic platform to allow many
`different material properties to be measured with minimal
`modification of the apparatus.
`SUMMARY OF THE INVENTION
`This invention provides an apparatus (or System) and
`method for testing materials in an array format using Sensors
`that contact the materials being tested. Accordingly, the
`present invention is directed to an electronically-driven
`Sensor array System for rapid characterization of multiple
`materials. A plurality of Sensors are disposed on a Substrate
`to form a Sensor array. Properties that can be measured
`include thermal, electrical and mechanical properties of
`Samples. Regardless of the property being measured or the
`Specific apparatus, the materials characterization System of
`
`35
`
`40
`
`45
`
`BACKGROUND
`Companies are turning to combinatorial materials Science
`techniques for developing new compounds or materials
`(including formulations, materials having different process
`ing histories, or mixtures of compounds) having novel
`physical and chemical properties. Combinatorial materials
`Science refers generally to methods and apparatuses for
`creating a collection of chemically diverse compounds or
`materials and to methods and apparatuses for rapidly testing
`or Screening Such compounds or materials for des