WO 2004/106581
`
`e
`
`PCT/US2004/0l4523
`
`of 51 ohms/sq. The roughness illustrated in Figure 9C can be characterized by an
`Ra=0.88 run and a Rmax of 19.8 nm.
`[0052)
`Figure 9D was deposited using 1.5 kW RF power, 300 W bias, 0 seem Qi,
`30 seem Ar at a temperature of 280 C. The layer grew to a thickness of 580 A in 100
`seconds of deposition time and exhibited a sheet resistance of 106 ohms/sq. The
`roughness illustrated in Figure 9C can be characterized by an Ra=0.45 nm and an
`Rmax of 4.6 nm.
`Utilizing the example depositions described herein, the roughness and
`(0053)
`resistivity of a transparent oxide film can be tuned to particular applications. In
`general, particularly high resistivities can be obtained, which are useful for touch
`sensitive devices. As shown in Table 3, the sheet resistance ranged from about 39
`0/sq for trial# 14 to a high of 12,284 0/sq for trial #1. Careful variation of the
`process parametf!'rs, therefore, allow control of sheet resistance over an e,i,.1remely
`broad range. Low resistivities can be obtained by adjusting the process parameters for
`uses in devices such as OLEOS and MEMS display devices. As is illustrated in Table
`3, the bulk resistivity can be controlled to be between about 2E-4 micro-ohms-cm to
`about 0.1 micro-ohms-cm. Additionally, other parameters such as refractive index
`and transparency of the film can be controlled.
`Further, deposition of transparent conductive oxide layers, for example
`[0054)
`ITO, can be doped with rare-earth ions, for example erbium or cerium, can be utiliz.ed
`to form color-conversion layers and light-emission sources. In some embodiments, a
`rare-earth doped target can be made in a single piece to insure uniformity of doping.
`Co-doping can be accomplished in the target
`(0055)
`Similar processes for other metallic conductive oxides can also be
`deveJoped. For example, deposition of zinc oxide films. Fw1her, as can be seen in
`the examples shown in Table 3, low temperature depositions can be performed. For
`example, transparent conductive oxides according to the present invention can be
`deposited at temperatures as low as about 100 °C. Such low temperature depositions
`can be important for depositions on temperature sensitive materials such as plastics.
`(0056)
`Other thin film layers according to the present invention include deposition
`of other metal oxides to form conducting and semi-conducting films. Thin films
`
`12
`
`Page 558 of 1053
`
`APPLIED MATERIALS EXHIBIT 1004 (Part 2 of 2)
`
`

`

`e
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`WO 2004/106581
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`PCT/US2004/0l4523
`
`'
`
`formed according to the present invention can be utilized in many devices, including,
`but not limited to, displays, photovoltaics, photosensors, touchscreens, and EMI
`shielding.
`
`Embodiments of the invention disclosed here are examples only.and are
`[0057)
`not intended to be limiting. Further, one skilled in the art will recognize variations in
`the embodiments of the invention described herein which are intended to be included
`within the scope and spirit of the present disclosure. As such, the invention is limited
`only by the folJowing claims.
`
`13
`
`Page 559 of 1053
`
`

`

`. Table I
`
`Slot#
`
`14
`15
`17
`19
`21
`1
`2
`3
`4
`5
`6
`
`Process
`
`1.51..-w/l 00w/200khz/2.2us/300s/20Ar/8002
`l.Skw/100w/200khz/2.2us/300s/20Ar/4002
`l.5kw/100w/200khz/2.2us/300s/20Ar/4002
`1.Skw/100w/200khz/2.2us/300s/20Ar/3602
`l .Skw/100w/200khz/2.2us/300s/20Ar/300,,
`1kw/100w/200khz/2.2us/300s/20Ar/ 8002
`1 kw/I 00w/200khz/2.21J,S/300s/20Ar/ 360,,
`lkw/1 OOw/200khz/2.2w300s/20Ar/ 320z
`l kw/1 OOw/200khz/2.2us/300s/20Ar/ 2802
`lkw/100w/200khz/2.2us/300s/20Ar/ 2402
`1kw/100w/200khz/2.2us/300s/20Ar/ 2802
`
`Tar2et Voltaee (V)
`Min
`Max
`244
`252
`254
`263
`260
`252
`263
`254
`268
`255
`224
`233
`· 231
`243
`242
`232
`243
`237
`243
`233
`231
`245
`
`Target Current (Amps)
`Mix
`Max
`5.94
`6.14
`5.9
`5.7
`5.16
`5.96
`5.72
`5.92
`5.9
`5.76
`4.5
`4.32
`4.3
`. 4.12
`4.28
`4.12
`4.22
`4.1
`4.34
`4.1
`4.3
`4.12
`
`... ..
`
`~
`0
`N
`C
`
`~ ... = °' '.It
`00 -
`
`e
`
`',:j
`I")
`
`e
`~ 00
`N = f
`c$ ... ...
`'.h t
`
`Page 560 of 1053
`
`

`

`'
`
`,,
`
`-. .,,
`
`Tablell
`
`Slot
`#
`
`Process
`
`Rs
`Rs unif
`(Ohms/ %
`Sq)
`
`Th (nm)
`
`Th std lsig
`
`Bulk Rho
`(µOhm-an)
`
`R.I (@632nm)
`
`R.I Unif(%) Comments
`
`1.5kw/100w/200khz/2.2µsi
`300s/20Ar/8002
`l.5kw/100w/200khz/2.2µs/
`300s/20Ar/4002
`1;5kw/100w/200khz/2.2f.lSJ
`300s/20Ar/4002
`l.5kw/100w/200khz/2.2µsJ
`300s/20Ar/3602
`l.5kw/100w/200khz/2.2µs/
`300s/20Ar/3002
`lkw/100w/200khz/2.2µs/
`300s/20Ar/8002
`llcw/100w/200khz/2.2µs/
`300s/20Ar/3602
`lkw/100w/200khz/2.2µs/
`300s/20Ar/3202
`lkw/100w/200khz/2.2µs/
`300s/20Ar/2802
`lkw/100w/200khz/2.2µs/
`300s/20Ar/2402
`lkw/100w/200khz/2.2µs/
`300s/20Ar/2802
`
`14
`
`15
`
`17
`
`19
`
`21
`
`1
`
`2
`
`3
`
`4
`
`5
`
`6
`
`38.59
`
`0.16
`
`1.980758
`
`0.000005
`
`transoarent
`
`94112
`
`2
`
`57.28
`
`0.51
`
`539073.5
`
`1.951452
`
`0.029342
`
`translucent
`
`33927 60.282
`
`58.48
`
`7335.32 72.49
`
`67.75
`
`22.3507 2.995
`
`80
`
`26.69
`
`36.4
`
`39.3
`
`44.02
`
`so
`
`45
`
`58.1031 7.467
`
`58.0992 10.566
`
`1.37
`
`1.03
`
`0.32
`
`0.13
`
`0.15
`
`0.24
`
`198405.1
`
`1.936166
`
`0.040957
`
`translucent
`
`49696.8
`
`1.980746
`
`0.000018
`
`translucent
`
`178.8 ·
`
`metallic
`
`1.980326
`
`0.00096
`
`transoarent
`
`1.980756
`
`0.000003
`
`transoarent
`
`1.980761
`
`0
`
`transparent
`
`1.98076
`
`0.000001
`
`transoarent
`
`290.5
`
`261.4·
`
`metallic
`
`metallic
`
`~
`0
`
`N ! 0
`00 ...
`
`0\
`'JI
`
`e
`
`e
`
`~
`I")
`
`N
`0
`0
`,la
`
`~ Y1
`~ -,la
`
`'JI
`N w
`
`Page 561 of 1053
`
`

`

`Tablefil
`
`~
`0
`N
`Q
`
`~ -Q
`Oil ...
`
`Ch
`•Jt
`
`Run
`<sec)
`100
`
`Trial
`14
`
`~
`Power ~
`(kW) w
`02 Ar
`3
`300
`3 60
`
`I..
`(oC)
`280
`
`Rs
`(Ohm.::/Sn)
`38.69
`
`B.§ (nQn-
`unit)
`4.07%.
`
`Thie
`Bulk Rho
`kness
`(uOhmcm)
`<A)
`4.64E-04 1200
`
`DepRa
`te
`(A/sec)
`12
`
`n
`1.864
`
`-0\
`
`16
`
`10
`
`4
`
`8
`
`2
`
`100
`
`100
`
`100
`
`100
`
`100
`
`3
`
`3
`
`1.5
`
`1.5
`
`1.5
`
`300
`
`3 30
`
`280
`
`56.90
`
`7.94%
`
`6.98E-04 1227
`
`1.888
`
`12.27
`
`100
`
`3 60
`
`280
`
`50.98
`
`11.89%
`
`1.933
`
`12.25
`
`100
`
`3 30
`
`280
`
`383.62
`
`21.72%
`
`2.09E-03
`
`2.016
`
`5.439
`
`300
`
`3' 30
`
`280
`
`504.02
`
`7.23%
`
`2.44E-03
`
`2.082
`
`4.835
`
`e
`
`Target
`N
`
`Tarnet/1
`
`9.86-
`10.42
`10.92-
`11.36
`
`5.98-6.32
`
`5.98-6.33
`.
`6.46-6.68
`
`100
`
`3 30
`
`280
`
`402.52
`
`26.80%
`
`6
`
`100
`
`1.5
`
`300
`
`0 30
`
`280
`
`106.21
`
`6.12%
`
`6.25E-04 1225
`543.
`9
`483.
`5
`520.
`7 2.056 5.207
`580.
`5
`
`6.17E-04
`
`1.945
`
`5.805
`
`2.lOE-03
`
`12
`
`15
`
`7
`
`1
`
`100
`
`100
`
`100
`
`100
`
`3
`
`3
`
`1.5
`
`1.5
`
`100
`
`4 30
`
`280
`
`374.34
`
`19.43%
`
`4.18E-03 1116
`
`1.917
`
`11.16
`
`300
`
`4 30
`
`100
`
`6264.69
`
`58.18%
`
`200
`
`4 30
`
`100
`
`7509.45
`
`44.14%
`
`100
`
`4 30
`
`100
`
`12284.82 112.55%
`
`2.95E-02
`
`4.78E-02
`
`6.81E-02 1087
`392.
`3
`389.
`1 2.236
`
`1.897
`
`10.87
`
`2.149 3.923
`
`3.891
`
`288-
`308
`265-
`275
`238-
`251
`239-
`250
`225-
`239
`237-
`250
`285-
`300
`282-
`304
`237-
`250
`238-
`250
`
`..
`
`5.98-6.38
`9.98-
`10.52
`10.00-
`10.62
`
`6.02-632
`
`6.04-632
`
`e
`.,,
`n
`~ en
`f
`<:> ... ... 'Jt t
`
`N
`Q
`
`Page 562 of 1053
`
`

`

`~
`
`Table m (Cont)
`
`11
`
`100
`
`100
`
`100
`
`100
`
`9
`
`5
`
`3
`
`13
`
`3
`
`3
`
`. 1.5
`
`100
`
`100
`
`200
`
`3
`
`0
`
`3
`
`60
`
`100
`
`631.77
`
`49.40%
`
`7.30E-03 1155
`
`1.958
`
`11.55
`
`30
`
`100
`
`43.78
`
`7.47%
`
`S.55E-04 1268
`
`1.945
`
`12.68
`
`10.96-
`11.38
`9.78-
`10.42
`
`60
`
`100
`
`1293.53
`
`14.82%
`
`5.88E-03
`
`454.8
`
`2.149 4.548
`
`6.46-6.68
`
`1.5
`
`100
`
`4 60
`
`100
`
`4154.43
`
`28.25%
`
`1.78E-02
`
`428.8
`
`2.211
`
`4.288
`
`C
`
`! N
`~ C
`CIC -
`°' u,
`
`e
`
`-....,
`
`100
`
`3
`
`200
`
`0 60
`
`100
`
`49.05
`
`7.24%
`
`6.16E-04
`
`.1256
`
`1.913
`
`12.56
`
`18
`
`100
`
`2.25
`
`100
`
`3 30
`
`100
`
`1476.79
`
`21.54%
`
`1.IOE-02
`
`744.5
`
`2.044 7.445
`
`17
`
`100
`
`1.5
`
`150
`
`0 60
`
`100
`
`157.23
`
`8.83%
`
`9.9IE-04
`
`630.5
`
`1.931
`
`6.305
`
`19
`
`100
`
`2.25
`
`150
`
`·3 60
`
`100
`
`526.72 .
`
`13.01%
`
`4.29E-03
`
`814.2
`
`2.021
`
`8.142
`
`266-
`273
`288-
`307
`225-
`235
`226-
`235
`264-
`275
`263-
`277
`225-
`231
`247-
`255
`
`6.44-6.64
`10.96-
`11.38
`
`8.08-8.56
`
`6.48-6.74
`
`8.78-9.14
`
`e
`
`"d
`
`~ V,
`N f
`c$ -~
`
`fJt
`~
`
`Page 563 of 1053
`
`

`

`WO 2004/106581
`
`e
`
`PCT/US2004/014523
`
`Oaims
`
`We claim:
`1. A method offonning a transparent conductive oxide film. comprising:
`depositing the transparent conductive oxide film in a pulsed DC reactive ion
`process with substrate bias; and
`controlling at least one process parameter to provide at least one characteristic
`of the conductive oxide film at a particular value.
`2. The method of claim 1, wherein contromng at least one process parameter includes
`controlling the o""ygen partial pressure.
`3. The method of claim 1, wherein the transparent conductive oxide film includes
`indiuim-tin oxide.
`4. The method _of claim 1, wherein the at least one characteristic includes sheet
`resistance.
`S. The method of claim 1, wherein the at least one characteristic includes film
`roughness.
`6. The method of claim 5, wherein the transparent conductive oxide film includes an
`indium-tin oxide film and the film roughness is characterized by Ra less than about 10
`nm with Rms ofless than about 20 nm.
`7. The method of claim 4, wherein the bulk resistance can be varied between about
`2xl 0-4 micro-ohms-cm to about 0.1 micro-ohms-cm
`8. The method -of claim l, wherein the at least one process parameter includes a
`power supplied to a target.
`9. The method of claim 1, wherein the at least one process parameter includes an
`oxygen partial pressure.
`10. The method of claim I, wherein the at least one process parameter includes bias
`power.
`11. The method of claim 1, wherein the at least one process parameter includes
`deposition temperature.
`12. The method of claim 1, wherein the at least one process parameter includes an
`argon partial pressure.
`13. The method of daim 1, further including supplying a metallic target
`
`18
`
`Page 564 of 1053
`
`

`

`e
`
`WO 2004/106581
`
`PCT/US2004/0U523
`
`14. The method of claim 1, further including supplying a ceramic target
`15. The method of claim 1, wherein the t:ramparent conductive oxide film is doped
`with at least one rare-earth ions.
`16. The method of claim 15, wherein the at least one rare-earth ions includes erbium.
`17. The method of claim 15, wherein the at least one rare-earth ions includes cerium.
`18. A method of depositing a transparent conductive oxide film on a substrate,
`comprising:
`placin~ the substrate in a reaction chamber;
`adjusting power to a pulsed DC power supply coupled to a target in the
`reaction chamber;
`adjusting an RF bias power coupled to the substrate;
`adjusting gas flow into the reaction chamber; and
`providing a magnetic field at the target in order to direct deposition of the
`transparent conductive oxide film on the substrate in a pulsed-de biased reactive-ion ·
`deposition process, wherein the transparent conductive oxide film e,chibits at least one
`particular property.
`19. The method of claim 18, wherein at least one particular property of the
`transparent conductive oxide film is determined by parameters of the pulsed-de biased
`reactive ion deposition process.
`20. The method of claim 19, wherein the at least one particular property includes
`resistivity of the transparent conductive oxide film.
`21. The method of claim 19, wherein the transparent conductive oxide film includes
`an indium-tin oxide film
`22. The method of claim 19, wherein the parameters include oxygen partial pressure.
`23. The method of claim 19, wherein the parameters include bias power.
`24. The method of claim 18, wherein the target can include at least one rare-earth
`ions.
`25. The method of claim 24, wherein the at least one rare-earth ions includes erbium
`26. The method of claim 24, wherein the at least one rare-earth ion includes cerbium.
`
`19
`
`Page 565 of 1053
`
`

`

`e
`
`WO 2004/106581
`
`PCT/US200.&/0l4523 .
`
`1/9
`
`. 12
`
`, 20
`
`15
`
`.... 14
`
`FILTl;R
`
`··po.c P.OWl;R
`
`.
`
`,,. .....
`
`. ....
`. \•
`
`54
`
`20
`
`. . ,· .
`. ..
`. ..
`.
`.
`
`Ar
`
`FiG~_ 1A
`
`. 52 .· .
`I
`
`. . : '
`--~-------------,_._~~
`
`•
`
`•
`
`I
`
`'19
`
`12
`
`"""
`
`I 6
`wu/HIW/HHD'1411~ 1.7
`1--------=t-,...;,
`
`•
`
`'
`
`FIG. 18
`
`SUBSTITUTE SHEET (RULE 26)
`
`Page 566 of 1053
`
`

`

`e
`
`WO 2004/106581
`
`PCT/US2004/01452J
`
`•
`
`2/9
`
`--->----
`
`-,
`
`X
`
`I
`I
`I
`
`I
`I
`I
`I
`I
`I
`I
`I
`I
`I
`
`I
`I
`I
`I
`I
`I
`
`I
`I
`I
`
`I
`
`:
`
`---------
`I -- --, I
`..
`N .
`1,.-.l-, ,
`·---- I
`.. - ,
`·- ---- ___ ;
`'
`
`'11:1'
`
`.
`
`.
`
`I
`I
`I
`
`I
`I
`I
`
`:
`
`I
`
`I
`I
`
`'
`
`\
`
`SUBSTITUTE SHEET (RULE 26)
`
`Page 567 of 1053
`
`

`

`PEAK SURFACE AREA SUMMIT ZERO CROSSING STOPHAND EXECUTE CURSOR
`ROUGHNESS ANALYSIS
`5.00
`
`PEAK SURFACE AREA SUMMIT ZERO CROSSING STOPBAND EXECUTE CURSO
`ROUGHNESS ANALYSIS
`5.00
`
`•
`
`•
`
`(./J
`
`C m
`(./J
`-f
`=i
`C
`-f m
`(./J
`:I:
`m
`m
`-f
`"i
`C r(cid:173)
`m
`N
`
`0, -
`
`2.50
`
`0
`030%Wds~ooo
`PEAK OFF AREA OFF
`l
`
`IMG.-
`IMG
`2.50 IIMG.
`
`IMAGE STATISTICS
`-RMS{Rij}~S.974 nm
`6.957 nm
`Rd
`93.310nm
`.
`RMAX
`BOX_SIATISTICS
`6.979 nm
`RMS {R9}
`MEAN ROUGHNESS (Pia) 6.956 nm
`93.299 nm
`O MAX HEIGHT (RMAX)
`5 ObJim BOXX DIMENSION
`3.796 pm
`aox DIMENS ON·
`·
`4.012
`SUMMIT OFF
`ZERO CROSS. OFF BOX CURSOR
`DIGITAL INSTRUMENTS NANOSCOPE
`SCAN SIZE
`5.000 JIM
`0.701ti Hz
`SCAN RATE
`NUMBER OF SAMPLES 512
`IMAGE DATA ·
`HEIGHT
`DATASCALE
`50.00nm
`a VIEWANGLE
`i) LIGHT ANGLE
`
`X 1.000mnOIV CC?
`od\_i5aix, Z 50.000nn/DIV w
`
`FIG. 3A
`
`2.SO
`
`O SLOT 19
`03051919.000
`PEAK OFF
`AREA OFF
`
`O I MAX HEIGHT (RMAX)
`
`a t1l ••• "'....
`
`IMAGE STATISTICS
`IMG RMS (Rq-)
`0.826 nm
`IMG
`Rd
`0.649 nm
`RMAX . · 13.488 nm
`2.50 IIMG
`BOX STATISIICS
`0.822 nm
`RMS (Rq}
`MEAN ROUGHNESS (Ra} 0.644 nm
`12.939 nm
`. 3.787 J1111
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`WO 2004/106581
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`SUBSTITUTE SHEET (RULE 26)
`
`Page 574 of 1053
`
`

`

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`
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`
`Defects in the images include but are not limited to the items checked:
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`0 BLACK BORDERS
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`Page 575 of 1053
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`

`

`r\
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`
`(12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT)
`
`(19) World Intellectual Property
`Orgunizalion
`lnLerna1ional Bureau
`
`I Riil lllllRI 11111111 ~Ill 111111111111111 ~ 1111111 IUll 11111 Hll 11111 ~II Ellll 11111111 Ill
`
`(43) International Publication Dale
`9 December 2004 (09.12.2004)
`
`PCT
`
`(10) International Publication Number
`WO 2004/106582 A2
`
`(51) J nternalional Patent Classification 7:
`14/08, 14134, BOIL:!1/316
`
`.
`
`C23C 14/14,
`
`(21) International Application Nwnber:
`P<.'T/US:!004/014524
`
`(22) International Flllng Date:
`
`21 May 1004 (11.05.1004>
`
`(25) FiUng Language:
`
`(26) PubUcalion Language:
`
`(30) Priority Data:
`60/473.375
`
`English
`
`English
`
`'.!3 May '.!003 (23.05.2003) US
`
`(71) Applicant (for all designated States e.xcepl US): SYM(cid:173)
`MORPHIX, INC. [US/US]; 1278 Reamwood Avenue,
`Sunnyvale, CA 94089-1:?33 (US).
`
`(81) Dcsignated States (unless otherwise i11dicated, for every
`kind of natimwl protection available): AE. AG, AL, AM,
`AT, AU, AZ, BA, BB. BG, BR, BW, BY, BZ, CA, CH, CN,
`CO. CR, CU, CZ, DE, DK, DM, DZ, EC, EE. EG, ES, Fl,
`GB, GD, OE. GH, GM. HR, HU, ID, IL, IN, IS. JP, KE,
`KG, KP, KR. KZ, LC, LK, LR, LS, LT, LU, LV, MA, MD.
`MG. MK, MN, MW, MX, MZ, NA, NI. NO, NZ, OM, PG,
`PH, PL. PT. RO, RU. SC, SD. SE, SG, SK, SL. SY, TJ, TM,
`TN, TR. li', Tl., UA, UG. US, UZ, VC, VN, YU, ZA. ZM.
`zw.
`
`(84.) Designated States (unless otherwise indica1ed, for every
`kind of regio,wl prote,:tiori available): ARIPO (BW, GH,
`GM, KE, LS, MW, MZ, NA, SD, SL, SZ, TZ, UG, ZM,
`ZW), Eurasian (AM, AZ, BY, KG, KZ, MD, RU. TJ, TM).
`European (AT, BE. BG, CH. CY, CZ, DE, DK, EE, ES, Fl,
`FR, GB, GR, HU, IE, IT, LU, MC, NI., PL, PT, RO, SE, SI,
`SK, TR), OAPI (BF, BJ, CF, CG, Cl, CM, GA, GN, GQ,
`GW, ML. MR. NE, SN. TD, TG).
`
`PubUshed:
`witlwu1 imema1ional search report and 10 be republished
`upon receipt of tltat report
`
`For two-le.Iler codes and other abbreviations. refer to the "Guid(cid:173)
`ance Notes on Codes and Abbreviations" appearing at tlte begin(cid:173)
`ning of each regular issue of tire PCT Gau.lie.
`
`= -!!!!!!!!I
`~ = !!!!!!!!! -iiiiiiiiiii -!!!!!!!!!!
`ii!!!l!ii! -= =(cid:173)
`
`(72) Inventors; and
`(75) Inventors/Applicants (for US 011/y): DEMARAY,
`Richard, Ernest [US/US]; 190 Fawn Lane, Portola Valley,
`CA 940:!8 (US). ZHANG, Hongmel [US/US]; 1330 Rod(cid:173)
`ney Drive, San Jose, CA 95118 (USl. NARASIMHAN,
`Mukundan [IN/US]; 293 Bluefield Drive, San Jose, CA
`95136 (US). MIWNOPOUWU, Vassillkl [GR/US];
`6160 Paseo Pueblo Drive, San Jose, CA 95120 (US).
`
`(74) Agent: GARRETJ', Arthur, S.; Finnegan, Henderson,
`Farabow, Garrell & Dunner, L.L.P., 1300 I Street N.W.,
`Washinton, D.C. :!0005-3315 (US).
`
`iiiiiiiiiii -== -= -= --== = = ~ -= iiiiiii -= =
`
`N
`I.() _______________ ___ __ ___ __ _ __ _ __ _ _ _
`QO
`
`~ 154) TIiie: ENERGY CONVERSION AND STORAGE foll.MS AND DEVICES BY PHYSICAL VAPOR DEPOSJ'nON OF TI(cid:173)
`'l"'""I TANTUM AND TITANIUM OXIDES AND SUB-OXIDES
`-..
`~
`.
`<:> (51) /\hslnu:t: High density oxide films are deposited by a pulsed-IX:, biased reactive spuuering process from a titanium containing
`<:> target 10 form high quality titanium containing oxide films. A method of fonning a titanium based layer or film according lo the
`N present invenlion includes depositing a layer of titanium containing oxide by pulsed-DC, biased reactive spuucring process on a sub-
`0 strale. In some embodiments, the layer is TIO~. In some cmhodimcnL~. the layer is a sub-oxide of Titanium. ln some i:mbodimenls,
`> the layer is Ti,Oy wherein xis between about I and about 4 and y is between about I and about 7. In some embodimenL~. the layer can
`~ be doped with om: or more rare-earth ions. Such layers are useful in energy and charge storage, and energy conversion technologies.
`
`BEST AVAILABLE COPY
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`WO 2004/106582
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`e
`
`PCT/US2004/0l 4524
`
`Energy Conversion and Storage Films and Devices by Physical Vapor Deposition
`of Titanium and Titanium Oxides and sub-Oxides
`
`Related Applications
`The present invention claims priority to U.S. Provisional Application Serial
`No. 60/473,375, "Energy Conversion and Storage Devices by Physical Vapor
`Deposition of Titanium Oxides and Sub-Oxides," by Richard E. Demaray and Hong
`Mei Zhang, filed on May 23, 2003, herein incorporated by reference in its entirety.
`
`Background
`
`1. Field of the Invention
`The present invention is related to fabrication of thin films for planar
`(0001)
`energy and charge storage and energy conversion and, in particular, thin films
`deposited of titanium and titanium oxides, sub oxides, and rare earth doped titanium
`oxides and sub oxides for planar energy and charge storage and energy conversion.
`2. Discussion of Related Art
`Currently, titanium oxide layers are not utilized commercially in energy
`(0002)
`storage, charge storage, or energy conversion systems because such layers are
`difficult to deposit, ~fficult to etch, are known to have large concentrations of
`defects, and have poor insulation properties due to a propensity for oxygen deficiency
`and the diffusion of oxygen defects in the layers. Additionally, amorphous titania is
`difficult to deposit due to its low recrystalization temperature (about 250 °C), above
`which the deposited layer is often a mixture of crystalline anatase and rutile
`
`structures.
`
`[0003]
`
`However, such amorphous titania layers, if they can be deposited in
`sufficient quality, have potential due to their high optical index, n-2. 7, and their high
`dielectric constant, k less than or equal to about 100. Further, they have substantial
`chemical stability. There are no known volatile halides and titania is uniquely
`
`resistant to mineral acids. Amorphous titania is thought to have the further advantage
`that there are no grain boundary mechanisms for electrical breakdown, chemical
`corrosion, or optical scattering. It is also well known that the sub oxides of titanium
`have unique and useful properties. See, e.g., Hayfield, P.C.S., "Development of a
`
`Page 577 of 1053
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`WO 2004/106582
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`PCT/US2004/0l4524
`
`New Material- Monolithic T40, Ebonix Ceramic", Royal Society Chemistry, ISBN:
`0-85405-984-3, 2002. Titanium monoxide, for example, is a conductor with a
`uniquely stable resistivity with varying temperature. Additionally, Tiz03, which can
`be pinkish in color, is known to have semiconductor type properties. However, these
`materials have not found utilization because of their difficult manufacture in films and
`their susceptibility to oxidation. Further, T407 demonstrates both useful electrical
`conductivity and unusual resistance to oxidation. T40,, however, is also difficult to
`fabricate, especially in thin film form.
`Additional to the difficulty of fabricating titanium oxide or sub oxide
`[0004)
`materials in useful thin film form, it also has proven difficult to dope these materials
`with, for example, rare earth ions, in useful or uniform concentration.
`Therefore, utilization of titanium oxide and suboxide films, with or
`[0005]
`without rare earth doping, has been significantly limited by previously available thin
`film processes. If such films could be deposited, their usefulness in capacitor, battery,
`and energy conversion and storage technologies would provide for many value-added
`applications.
`Current practice for construction of capacitor and resistor arrays and for
`thin filqi energy storage devices is to utilize a conductive substrate or to deposit the
`metal conductor or electrode , the resistor layer, and the dielectric capacitor films
`from various material systems. Such material systems for vacuum thin films, for
`example, include copper, aluminum, nickel, platinum, chrome, or gold depositions, as
`well as conductive oxides such as ITO, doped zinc oxide, or other conducting
`materials.
`[0007) Materials such as chrome-silicon monoxide or tantalum nitride are known
`to provide resistive layers with I 00 parts per million or less resistivity change per
`degree Centigrade for operation within typical operating parameters. A wide range of
`dielectric materials such as silica, silicon nitride, alumina, or tantalum pentoxide can
`be utilized for the capacitor layer. These materials typically have dielectric constants
`k ofless than about twenty four (24). In contrast, Ti02 either in the pure rutile phase
`or in the pure amorphous state can demonstrate a dielectric constant as high as 100.
`See: e.g., RB. van Dover, "Amorphous Lanthanide-Doped Ti02 Dielectric Films,"
`
`[0006]
`
`2
`
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`e·
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`PCT/US2004/014524
`
`Appl. Phys Lett., Vol. 74, no. 20, p. 3041-43 (May 17, 1999).
`It is well known that the dielectric strength of a material decreases with
`[0008]
`increasing value of dielectric constant k for all dielectric films. A 'figure of merit' (
`FM) is therefore obtained by the product of the dielectric constant k and the dielectric
`strength measured in Volts per cm of dielectric thiclmess. Capacitive density of
`10,000 to 12,000 pico Farads /mm2 is very difficult to achieve with present
`conductors and dielectrics. Current practice for reactive deposition of titanium oxide
`has achieved a figure-of-merit, FM, of about 50 (kMV/cm). See J.-Y. Kim et al.,
`"Frequency-Dependent Pulsed Direct Current Magnetron Sputtering of Titanium
`Oxide Films," J. Vac. Sci. Technol. A 19(2), Mar/Apr 2001.
`(0009]
`Therefore, there is an ongoing need for titanium oxide and titanium sub(cid:173)
`oxide layers, and rare-earth doped titanium oxide and titanium sub-oxide layers, for
`various applications.
`
`Summary
`In accordance with the present invention, high density oxide films are
`[0010)
`deposited by a pulsed-DC, biased, r~ctive sputtering process from a titanium
`containing target. A method of forming a titanium based layer or film according to
`the present invention includes
`depositing a layer of titanium containing oxide
`by pulsed-DC, biased reactive sputtering process on a substrate. In some
`embodiments, the layer is Ti~. In some embodiments, the layer is a sub-oxide of
`Titanium. In some embodiments, the layer is TixOy wherein x is between about 1 and
`about 4 and y is betwee~ about 1 and about 7.
`In some embodiments of the invention, the figure of merit of the layer is
`[0011)
`greater than 50. In some embodiments of the invention, the lay~r can be deposited
`between conducting layers to form a capacitor. In some embodiments of the
`invention, the layer includes at least one rare-earth ion. In some embodiments of the
`invention, the at least one rare-earth ion includes erbium. In some embodiments of
`the invention, the erbium doped layer can be deposited between conducting layers to
`form a light.:.emitting device. In some embodiments of the invention, the erbium
`doped layer can be an optically active layer deposited on a light-emitting device. In
`some embodiments of the invention, the layer. can b~ a protective layer. In some
`
`3
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`
`embodiments, the protective layer can be a catalytic layer.
`
`[0012)
`
`In some embodiments of the invention, the layer and a Ti02 layer can be
`
`deposited between conducting layers to form a capacitor with decreased roll-off
`
`characteristics with decreasing thickness of the Ti02 layer. In some embodiments, the
`
`Ti02 layer can be a layer deposited according to some embodiments of the present
`invention.
`
`[0013]
`
`These and other embodiments of the present invention are further
`
`discussed below with reference to the following figures.
`
`Short Description of the Figures
`
`[0014]
`
`Figures IA and lB illustrate a pulsed-DC biased reactive ion deposition
`
`apparatus that can be utilized in the deposition according to the present invention.
`
`(0015]
`
`Figure 2 shows an example of a target that can be utilized in the reactor
`
`illustrated in Figures IA and IB.
`
`[0016]
`
`Figures 3A and 3B illustrate various configurations oflayers according to
`
`[0017]
`
`embodiments of the present invention.
`Figures 4A and 4B illustrate further various configurations M layers
`according to embodiments of the present invention.
`
`(0018]
`
`Figure 5 shows another layer structure involving one or more layers
`
`according to the present invention.
`
`(0019]
`
`Figure 6 shows a transistor gate with a TiOy layer according to the present
`
`invention.
`
`(0020)
`
`Figure 7 illustrates the roll-off of the dielectric constant with decreasing
`
`film thickness.
`
`[0021]
`
`Figure 8 illustrates data points from a bottom electrode that helps reduce or
`
`eliminate the roll-off illustrated in Figure 7.
`
`[0022)
`
`Figures 9A and 9B illustrate an SEM cross-section of a T40, target
`
`obtained from Ebonex™ and an SEM cross section of the T406.8 film deposited from
`
`the Ebonex™ target according to the present invention.
`
`[0023]
`Figure 10 shows the industry standard of thin-film capacitor performance
`in comparison with layers according to some embodiments of the present invention.
`
`[0024)
`
`Figure 11 shows the performance of various thin films deposited according
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`e
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`WO 2004/106582
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`e
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`PCT/US2004/01"524
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`to the present invention in a capacitor structure.
`
`[0025]
`
`Figure 12 shows a cross-section TEM and diffraction pattern amorphous
`
`and crystalline layers of Ti02 on n++ wafers.
`Figure 13 shows a comparison of the leakage current for Ti02 films
`(0026]
`
`according to embodiments of the present invention with and without erbium ion
`
`doping.
`
`Figures 14A and 14B show a photoluminescence signal measured from a
`[0027)
`5000 A layer of 10% erbium containing Ti02 deposited from a 10% erbium doped
`TiO conductive target and a photoluminescence signal measured from the same layer
`
`after a 30 minute 250 °C anneal.
`
`(0028]
`
`In the figures, elements having the same designation have the same or
`
`similar functions.
`
`Detailed Description
`
`[0029] Miniaturization is driving the form factor of portable electronic
`
`components. Thin film dielectrics with high dielectric constants and breakdown
`strengths allow production of high density capacitor arrays for mobile
`communications devices and on-chip high-dielectric capacitors for advanced CMOS
`processes. Thick film dielectrics for high energy storage capacitors allow production
`
`of portable power devices.
`
`[0030)
`
`Some embodiments of films deposited according to the present invention
`
`have a combination of high dielectric and high breakdown voltages. Newly
`
`developed electrode materials allow the production of very thin films with high
`
`capacitance density. The combination of high dielectric and high breakdown volt