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1 1974, Si wafer 200 mm 300 mm. Si wafer, Si wafer 3. Si CVD(Chemical vapor deposition). Si wafer process tube, liner tube, wafer wafer carrier boat, dummy wafer, edge ring, fork cantilever loading, susceptor, heater. (quartz), (SiC), (Al 2O 3), (AlN), 2. Si wafer,,,,. 300 mm Si wafer.,.,. Si graphite quartz, Al 2O 3,, AlN, BN, Si 3N 4,, Si. 1000, 38

2 900 CVD,, Si wafer,.,,.,., 15. Table 1 Fig. 1 SiC/Si, CVD- SiC, HF/HNO 3. CVD SiC 0.1 ppm, SiC/Si CVD SiC 3.0~3.2 g/cm 3 quartz,., CVD Si de-vitrification flaking., Fig. 1 LP CVD. 3.1 Table 1. SiC SiC/Si (Si impregnation) CVD SiC Fe Ni Cu < Ca Al (ppm) Na < α-sic+si β-sic α-sio 2 (kg/m 3 ) (%) (MPa, RT) (MPa, RT) (/K, RT-1200 ) 4.5* * *10-7 (W/mK) RT (ohm m) 1*10-3 6*10 3 3*10 6 HF (10 % HF ) Fig. 1. HF/HNO3, Si SiC β-sic α-sic,. Acheson 39

3 Table 2. Manufacturer Loaction Capacity(metric tons) Norton Advanced Ceramics Canada 40,000 Exolon-ESK Hennepin 42,000 Treibacher Canada 18,000 Sicven Venezuela 15,000 Casil Brazil 28,000 Alcoa Brizil 12,000 Casale Argentina 4,000 Norton AS Norway 67,000 ESK Netherland 50,000 Lonza Switzerland 8,000 Nabaro Spain 16,000 Pacific Rundum Japan 7,000 Yakushima Denko Japan 24,000 Norton Venezuela 20,000 : annual mineral review, Am. Ceram. SoC. Bull., 75(6),153-4 (1996) Acheson furnace (SiO 2) (petrolium coke) 2200 ~ 2400 α- SiC ingot. SiO 2 + 3C SiC + 2CO α-sic ingot.,. Table 2. Lutch ceramic HCl, α- Table 3. HCl, Kuzenetsov N.N. Jokhov A.A. Toshiba ceramics Co. halogen gas halogen /hydrogen halide 1), graphite Table 4. CVD (chemical vapor deposition) CVD Table 3. Halogen purification graphite metallic impurity level (ppm) Al B Cu Fe Mg Mn Ti Ca Ni V no 2 1# no no 5 2# no no # no no 0.6 4# no # untreated sample, #-treated sample 1 - carbon MPG carbon G graphite thermal isolation NUGM 4 - graphite thermal isolation UTP green technical SiC with middle size grains 120 µm 1) Tahashi Tanaka et al, Method of manufacturing parts for use to the heat processing furnace, U.S. papent 4,619,798 40

4 Table 4. Lucth ceramics Impurities Impurities Impurities Element Element Element content(ppm) content(ppm) content(ppm) Mn 0.16 Mo <0.5 Au <1 Dy Cu 3 Cr 6.1 U <0.01 W 0.52 Ni 1.3 Th 0.15 Na 4.1 Co 0.2 La <0.05 K 2.2 Fe 3.7 Sb <0.2 Sc <0.05 Hf Ta 0, 011 Zr <0, 5 Ir <0, 01 : G.I. Babayants, Special purity substances, Microelectronics, Jan, 17, 1996 & CVD. SiCl 2, SiH 2 CH 4, C 3H 4, CCl 4 CVD CH 3SiCl 3, (CH 3) 2SiCl 2, Si(CH 3) 4.. 7SiCl 3 + C 7H H 2 7SiC + 28HCl SiH 4 + CH 4 SiC + 4H 2 CH 3SiCl 3 SiC + 3HCl cabothermal reduction, SiO 2 β-sic. (ethyl silicate) β-sic. Table 5 Bridgestone Co. β-sic.. Table 5. (ethyl silicate) (phenol) (formaldehyde) β- Na K Ca Fe Ni Cu Cr V A <1 <1 <1 <1 <1 <1 <1 <1 B 4 <1 <1 5 <1 <1 <1 <1 : ,, CVD SiC. (pressureless sintered or hot pressed SiC) 1970 G.E. Prochazka B C C B 4C, BN, BP boron, Al, AlN, Al 4C 3, AlB 2 Al. Omori Takei.. Al 2O 3- Y 2O 3 Al 2O 3-Y 2O 3-CaOAlN-Y 2O 3. Alliegro Fe, Al, Al 2O 3 wt % 41

5 . Al, Fe, W, B, AlN.,,,., 1~5 wt %.. Si Si-SiC CVD SiC coating forks plate Si wafer handling, plate edge ring lapping plate.. Toshiba ceramics (CERASIC) Ceradyne Ceralloy146., Bridgestone β- PureBeta-S, Table 6 Bridgestone PureBeta-S grade. Bridgestone PureBeta-S grade ppb, CVD. PureBeta-S dummy wafer, heater related products, etching Table 6. Bridgestone PureBeta-S grade Element Bulk(ppm) Surface (10 10 atoms/cm 2 ) B Na < Al K <0.01 <DL Ca 0.07 <DL Ti 0.01 <DL Cr <0.03 <DL Mn <0.001 <DL Fe Ni Cu <0.006 <DL Zn <0.01 <DL W <0.002 <DL - Bulk : based on glow discharge mass spectrometry(gd-ms) - Surface : based on total reflection X-Ray fluorescence analysis(txrf) - DL : minimum limit of detection : Table 7. Toshiba ceramics CERASIC Bridgestone PureBeta-S grade Company BRIDGESTONE Toshiba Ceramics Product name PUREBETA-S CERASIC Structure β-sic α-sic Density(g/cm 3 ) Vickers Hardness Bending strength(mpa) Elasticity(GPa) Poisson s ratio Thermal expansion(10-6/k) Thermal conductivity(w/m.k) Electrical/volume resistivity(.m) equipments parts, ion implanter parts, CVD equipment parts. Table 7 Toshiba ceramics CERASIC Bridgestone PureBeta- S grade, PureBeta-S grade CERASIC. (recrystallized SiC). 42

6 ., ,, 10~30 %. (binder),, 2000 ~ 2400, 2200,. Si. Si SiO 2 (wetting angle) 90 (non-wetting) SiO 2 Si Si Si Si Si-SiC. Table 8 Si,. Si Si Si 1420 Table 8. Si Noton Asahi ceramics AGEM Corp. Saint-Gobain ( ) (Roiceram HS-U) (Agem) (CRYSTAR) Fe Al Ni Ca Cu <1 < Na <1 < Ti Mg - < K - < (ppm) Zn - < Zr V Cr - <0.6 - Mn - < α-sic+si α-sic+si α-sic+si (g/cm 3 ) (%) - - < 1 % (MPa) (GPa, RT) (RT-1000 ) *10-6 / (W/mK) RT (ohm cm) 0.1 : (reaction bonded SiC, RBSC) / Si (β-sic) Si SiC-Si. Si Si Si. Si 1450~1600, 43

7 Table 9. Process Preform materials Characteristics REFEL α-sic /carbon powder Capillary Climb & reaction Capillary Climb & reaction Shortening the infiltration time by using carbon fiber / C fiber SILCOMP C-precursor / Large and thin-shelled structure having SiC fiber complex curvature can be easily produced Large scale structure can be produced SiC powder / without forming preform Inex Si powder / SiC/Si/C mixture is consolidated by a Carbon powder moving hot zone (Induction heating) Impregnation of Si melt using graphite a continuous α-sic/carbon feeder Si infiltration powder continuous process & large scale complex process shaped articles can be easily produced.., Si Si Si. REFEL process, SICOMP process, Inex process continuous reaction sintering process Table 9. CVD,, CVD heater Si wafer handling. ( ). ( ). handling, CVD. Toshiba ceramics TPSS grade Norton Saint- Gobain CRYSTAR. Toshiba ceramics TPSS grade, U-grade α-grade., Maicom-Quarz Gmbh 8 inch Si wafer. Bridgestone PureBeta-R grade β-sic 1400 CVD., Purebeta-R grade CVD. Acheson α-sic α-sic β- SiC. Table 10 44

8 . CVD (chemically vapor deposited SiC, CVD-SiC) Si C 1200~1500. CVD, (mirror),. Si C (precursor) Silane Si:C (stoichiometric) 1:1 MTS(methyl trichlorosilane, CH 3SiCl 3), (CH 3) 2SiCl 2., CVD Si C SiC l4/ch 4. CVD 2 Si., CVD Si : C 1 : 1 MTS. MTS carrier gas H 2 CVD. CH 3SiCl 3(g) + excess H 2 SiC(s) + 3HCl(g) + excess H 2 1 : Carbon containing species : CH 3 radical, CH 4 Silicon containing species : SiCl 3 radical, SiCl 3, SiCl 2 2 : Si, C Table 10. Toshiba Toshiba Maicom Quarz Bridgestone/ / ceramics/ ceramics/ GmbH/SiC- PureBeta-R TPSS-U TPSS-alpha Silicon carbide Fe Al Ni Ca Cu <0.01 < Na <0.2 < Ti Mg - <0.2 - K - < Zn - <0.4 - (ppm) Zr V Cr - < Mn - < B 0.04 W 0.01 α-sic+si α-sic+si α-sic+si SiC + Si (g/cm 3 ) (%) < 1 % (MPa) 1500 (MPa, RT) (GPa, RT) 280 (RT-1000 ) 4.8*10-6 / 4.2*10-6 / (W/mK) RT specific heat (j/g K) 0.68 (ohm cm) CH 4 C + H 2 SiCl 3 + 3/2 H 2 Si + 3HCl 3 : Si + C SiC thermal CVD, plasma enhanced CVD, laser CVD, electron beam assisted CVD, CVD thermal CVD. CVD CVD hot-wall type cold-wall type. CVD 45

9 Table 11. CVD Application Characteristic/Property Benefits Low Etch Rate Longer component life than quartz or silicon in fluorine or chlorine based plasmas Longer component life than reaction bonded or hot pressed SiC in fluorine based plasmas High purity( %+) No aluminum contamination issue as when using alumina components No sintering aid additives No matallic contamination caused by sitering adis as in Hot pressed or direct sintered SiC Plasma Etch Homogeneous Structure Low particle generation No Secondary phases Low Resistivity (1-10 ohm-cm) available Useful for applications requiring RF coupling High purity( %+) No contamination of water or processing chamber High Thermal Conductivity High thermal shoch resistance (300 W/m K) Exellent wafer temperature uniformity High Elastic Modulus (466 Gpa), Rapid Allows very thin cross sections and low mass, resulting in increased wafer thru-put High Specific Stiffness Thermal Elastic Modulus nearly independent Flatness retained during and after high temp. use, aids in even heating Epitaxy of Temp ( ) and processing of wafer High Chemical Resistance Little or no degradation in HCl or HF chamber cleaning cycles Solid, Not a coating Components cannot pin-hole as CVD coated graphite parts do, so lifetime of the component is extended and contamination of wafers is prevented High purity( %+) No contamination of water or processing chamber High Thermal Conductivity Rapid (300 W/m K) High thermal shoch resistance Thermal High Elastic Modulus (466 Gpa), Processing High Specific Stiffness Allows very thin cross sections and low mass, resulting in increased wafer thru-put Elastic Modulus nearly independent of Temp (435 Gpa@ 1000 ) Flatness retained during and after high temp. use, aids in even heating and processing of wafer. CVD Si wafer., CVD Si. Table 11 CVD. CVD CVD. CVD Rohm and Hass advanced materials division CVD SILICON CARBIDE. CVD SILICON CARBIDE Rhom and Hass Advanced Material bulk CVD, ( > %) β-sic,. CVD SILICON CARBIDE Tables 12, 13,. CVD CVD 50~70, CVD Si, Toshiba ceramics, Asahi ceramics, Norton Saint-Gobain. 46

10 Table 12. CVD SILICON CARBIDE PROPERTIES TYPICAL VALUES (Room Temperature) Crystal Structure FCC(face-centered cubic b-phase)polycrystalline Sublimation Temperature (degrees C) ~ 2700 Grain size (microns) 5-10 Density (grams per cc) 3.21 Hardness (kg per square mm) - - Knoop (500 g load) Vickers (500 g load) 2500 Chemical Purity > % SiC Flexural Strength, 4-point (MPa/Ksi) Mil Std 1942 B - - At Room Temperature 470 / 68 - At / 84 Weibull Parameters - - Modulus, m Scale Factor, beta (Mpa/Ksi) 462 / 66 Fracture Toughness, KIC values - - Micro-indentation (MN m -1.5 ) Controlled Flow (MN m -1.5 ) 2.7 Elastic Modulus (GPa/106psi) - - Sonic 466 / 68-4 point Flexure 461 / 67 Coefficient of Thermal Expansion (1/K) - - At Room Temperature Room Temperaure to Heat Capacity (J/Kg-K) 640 Thermal Conducitivy (W/m-K) 300 Poisson s Ratio 0.21 Polishability (Optical profilometer) <3 Angstroms RMS Low < 1 ohm-cm Electrical Resistivity Standard ohm-cm High > 1000 ohm-cm POCO speciality materials CVD vapor phase diffusion reaction in-situ vapor solid reaction graphite SiO SiC SUPERSiC. SiO 2 + C SiO(g) + CO(g) SiO(g) + 2C SiC(s) + CO(g) SUPERSiC β-sic, % CVD SUPERSiC MTS H 2 CVD Table 13. CVD SILICON CARBIDE Element GDMS NAA Element GDMS NAA Li <3.2 - Rh <3.6 - Be <5.9 - Pd <25 - B Ag <20 <0.047 Na Cd <150 <0.57 Mg <34 - In <22 <0.097 Al Sn <29 <4.1 P 28 - Sb < S 88 - I <63 - K <9.4 <21 Te <26 - Ca <5.8 <840 Cs <13 < Sc <0.64 < Ba <5.7 <2.2 Ti <4.2 <1400 La <1.2 < Cr Ce <9.8 <0.038 V <1.4 - Eu Mn <3.9 - Tb - < Fe <40 <5 Yb - <0.021 Co <4.0 <0.67 Nd <7.3 - Ni < Hf <6.1 < Cu < Ta - < Zn < W < Ga <29 <0.16 Re <5.3 - Ge <28 - Os <6.3 - As < Ir <8.5 < Se < Pt <9.6 <19 Br - <0.02 Au Rb <11 <0.36 Hg <43 <0.02 Sr <1.1 <3.9 Tl <21 - Y < Pb <7.1 - Zr <3.2 <4.5 Bi <6.1 - Nb <3.5 - Th <0.61 <0.007 Mo < U <0.42 <0.039 Ru < : Typical Trace Element Impurities in Parts per Billion by Weight using Gas Discharge Mass Spectrometry (GDMS) and Neutron Activation Analysis (NAA)., CVD. SUPERSiC graphite SiC. Graphite 2500 Fluorine chlorine-radical, CCl 2F 2, halogenhalogen, Toshiba ceramics 5ppm Ultra-puricfication. 47

Horizontal vertical assembly processing tube, liner tube, cantilever paddles system, pedestals, Si wafer carrying boat (or conti boat), dummy wafer,

11 Table 14. : (800~1200 ) (SiO 2) Horizontal/ (Oxidation & vertical : Furnace( ). Diffusion) Furnace (Horizontal) (Vertical). AP- CVD LP- CVD (CVD) PE- CVD gas gas Implanter. Sputter. (Al). (Thin Film) (Na), Grinder. Etcher. (Etch) Stripper. Station 3.2 Table 14.,, handling.,. : (Diffusion)/(oxidation), CVD, ion implantation - /. Horizontal vertical assembly processing tube, liner tube, cantilever paddles system, pedestals, Si wafer carrying boat (or conti boat), dummy wafer, thermo-couple sheath. Figs. 2, 3. Si wafer 1000~2500mm, processing liner tube Si wafer 150~450 mm. Processing liner tube. Si wafer boat Fig. 2.,. Fig. 3.,. 48

12 wafer Si wafer Si wafer. Dummy wafer Si wafer Si wafer carrying boat Si wafer. Cantilever paddles system cantilever liner tube Si wafer carrying boat loading system. Pedestals heat barrier Si carrying boat. - CVD LP(low pressure)-cvd, AP(atomospheric pressure)-cvd, PE(Plasma enhanced)-cvd. CVD. Single wafer process Si wafer susceptor, electrode heating system, susceptor, electrode heat Fig. 4. Norton Saint- Gobain, CVD CRYSTAR Si wafer boat Si waferboat Si wafer slip Fig Ion implantation Single wafer CVD ,. processing tube liner tube, 1350., processing tube liner tube device. 300mm Si wafer. boat liner tube LP-CVD spalling., slot. dummy wafer LPCVD. dummy wafer 1~10, dummy wafer dummy wafer,,. dummy wafer, CVD CVD. Fig. 6 Bridgestone β-sic heater dummy wafer. : (etching), handling Si wafer handling,,, guide ring, edge ring, wafer chamber, fork, Robot arm, focus ring, electrode, holder. Fig. 7 Bridgestone electrode edge ring. 49

13 Fig. 4. LP-CVD vertical wafer boat gas injector. Fig. 5. LPCVD vertical wafer boat. Dummy Wafer Heater Fig. 6. Dummy wafer heater. (Bridgestone PureBeta-S).,.,,.,,,, Si wafer LP-CVD,,.,.,.,.. Electrode Edge Ring Fig. 7. electrode edge ring. (Bridgestone PureBeta-S) Si wafer 4.1 Acheson,. 50

14 ., Si wafer CVD. handling ppb., CVD., CVD. Bridgestone PureBetar-S PureBeta-R. Bridgestone CVD PureBeta-S, R grade CVD., -SiC., - -SiC.. 4.2, Si 30., Si wafer 300 mm,.,.,. CVD, dummy wafer. Bridgestone PureBeta CVD,., 51

15 Si.,. 4.3, key fact. 300 mm Si wafer,., Norton Saint-Gobaind LP-CVD vertical Si wafer boat., 300 mm Si wafer. KISTI /. 1. N. Kageyama, Silicon carbide products for silicon semiconductor manufacturing, Ceramics, jpn, 30[5] (1995) 2. J. A. Tomanovich, LPCVD components trend toward SiC, Solid State Tech., , (1997). 3. K. Segawara, Introductory remarks on ceramics for silicon semiconductor manufacturing VLSI fabrication and its related ceramics, Ceramics, jpn, 30[5] (1995). 4. K. Shiraishi, Silica glass for semiconductor process, Ceramics, jpn, 30[5] (1995). 5. Chang-Bin Lim, Microstucture Control or Reaction- Sintered Silicon Carbide, Ph. D. Thesis, TiT (1989) 6. J. L. Fitzjohn and W. L. Holsten, Divergent Flow in Chemical Vapor Deposition Reactors, J. Electrochem.Soc., 137[2] (1990) 7. Brochers, Midland Materials Research, Inc., Midland, Michigan, U.S.A. 8. S. R. Billington, J. Chown and A.E.S. White, P.1934 in Special Ceramics deited by J.J. Bueke et al. (1974) 9. C. E. Morosanu, Thin Films by Chemical Vapor Deposition Elsevier J. Chin. P. K. Gantzel and R. G, Hudson, The structure of Chemical Vapor Deposited Silicon Carbide Thin Solid Films, 40, (1977). 11. R. A. Alliegro, L. B. Coflin and J.R. Tinklepaugh : J. Am. Ceram. Soc., 39, 386 (1956) 12. S. Prochazka and R. J. Charles :Am. Ceram. Bull., 52, 885 (1973) 13. S. Prochazka and : Ceramics for High Performance Applications (edited by J.J. Burke, A. E. Gorum and R. N. Katz), Brook Hill Pub. Co., p253 (1974) 14. S. Prochazki : special ceramics 6(edited by P. Popper),B. Ceram. R. A., Stoke-on trent, p.171 (1975) 15. M. G. Rogers : Special ceramics 5, p A. W. C. Van Kemenade and C. F. Stemfoort, On the Formation of -SiC form Pyrolysis of CH3SiCl3 in Hydrogen, J. Cryst. Growth, 12, (1972). 17. S. Motojima, H. Yagi and N. Iwamori, Chemical Vapor Deposition of SiC and Some of its properties, J. Mater. Sci. Lett., 5, (1986)

16 Ph.D Postdoctoral Fellow Postdoctoral Research Scientist Postdoctoral researcher

Ceramic & Advanced Material News 2 0 1 6. 0 4 한다 고 말했다. 권 교수팀은 이 소재로 LED 를 대체할 수 있는 제품을 만드는 것을 1차 목 표로 연구를 진행 중이다. 한국도자기, 경영난 타파 노력 국내 1위 도자기 제조업체인 한국

Ceramic & Advanced Material News 2 0 1 6. 0 4 한국세라믹연합회, 세라믹산업 자격설계 보완 한국세라믹연합회(회장 신재수)가 세라믹 산 업 분야 국가직무능력(NCS) 및 신직업자격 보완 을 진행한다. 지난달 25일, 한국세라믹 연합회는 세라믹 관련 전문가 10여 명과 함 께 사업 세부계획에 대해 논의했다. 연합회는 현재 국가직무능력