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Thin-Film Inorganic HighPerformance Devices via Additive Processing 4/5/2005 Inorganic Devices via Additive Processing Thin-Film Inorganic High-Performance Devices via Additive Processing Semiannual Review, April 2005 Chemistry – Jeremy Anderson, Stephen Meyers, Jason Stowers, Douglas Keszler Electrical Engineering – David Hong, John Olson, Hai Chiang, John F. Wager Chemical Engineering – Yu-jen Chang, Alex Chang 2 Inorganic Devices via Additive Processing Goals: • Demonstrate low-temperature fabrication (T < 100oC) • Achieve high performance in transistor mobility (μFE 50 cm2/Vs) • Complementary n- and p-type behavior in solution processed semiconductors 3 Inorganic Devices via Additive Processing Process: • Materials identification and invention • Literature precedents, physical and chemical models • Physical vapor deposition of thin films • Chemical process development • Single-source precursors • Nanolaminates • Printing • Device characterization and development • Transistors and capacitors 4 Inorganic Devices via Additive Processing Results: • Enhanced performance in HafSOx dielectric • New low K phosphate dielectric • New single-source precursor for near roomtemperature deposition of ZnO • Nanolaminates for toolbox approach to multicomponent materials and control of function • Use of nonaqueous solutions for ink-jet printing • Solution processed transistor (dielectric + channel) • Materials/Process Studies: Physical vapor deposition of new oxide transistors and p-type 5 oxides Solution Phase Deposition of Inorganic Thin Films 6 Strategies for Solution Based Thin Films 1. Deposit film as solid phase constituents - no extra anneal 2. Add organic thickener - burnoff required 3. Add additional ions - incorporate into film, rinse, or burnoff 4. Polymerize material on surface - vaporize solvent 7 Importance of Liquid/Solid Thin Film Conversion Parameters: • Temperature • Ramp rate • Ambient • Film thickness • Composition 400ºC 600ºC 8 Higher Permittivity Dielectric by Layering Technique medium k (amorphous) example: Hafsox medium k (amorphous) high k (crystalline) medium k (amorphous) high k (crystalline) high k (crystalline) example: TiO2, Ln2O3 medium k (amorphous) high k (crystalline) medium k (amorphous) substrate 9 Buffer Films for Control of MOSFET conduct conduct channel dielectric dielectric buffer conduct conduct channel channel buffer dielectric conductor conductor substrate substrate Solution-Based Deposition Jeremy Anderson Stephen Meyers Jon Olson Hydrated oxides -no layer mixing- oxide #1 oxide #2 anneal July 18, 2015 July 18, 2015 12 HP Confidential GSH, page 12 Hydrated oxides -complete layer mixing- oxide #1 oxide #2 anneal ternary oxide July 18, 2015 July 18, 2015 13 HP Confidential GSH, page 13 Demonstration of smooth reproducible thin layers Hafsox Zircsox substrate Film thickness demonstrated at 5 nm. July 18, 2015 July 18, 2015 14 HP Confidential GSH, page 14 X-ray reflectivity for Hafsox/Zircsox multilayer film 8 log (cps) 6 4 2 0 0 July 18, 2015 July 18, 2015 2 4 6 2 theta HP Confidential 8 10 15 GSH, page 15 Conversion liquid film to solid film L M polymerization H OH L H M M O L M M M M O M M O L O M M O M O M O M M O M O M O O M O M O M July 18, 2015 July 18, 2015 combustion L L O O H M M M L L O M 16 HP Confidential GSH, page 16 Rapid Low Temperature Reaction • Dense film formation requires extended bond formation • Polymerization process should have low activation energy July 18, 2015 July 18, 2015 17 HP Confidential GSH, page 17 Rapid Low Temperature Reaction: Hafsox/La Reaction Hafsox 325º C HfOCl2 + x H2SO4 + (1-x) H2O HfO2-x(SO4)x + 2 HCl Reaction Hafsox/La 325º C HfOCl2 + x La2(SO4)3 + H2O HfLa2xO2(SO4)3x + 2HCl July 18, 2015 July 18, 2015 18 HP Confidential GSH, page 18 Rapid Low Temperature Reaction: Tin oxide phosphate (TOP) 600º C SnCl4 + H2O2 + 2H2O 600ºC SnO2 + O2 + 4HCl No transistor behavior 500º C 500ºC SnCl4 + x H3PO4 + (2-3x/2) H2O SnO1.7(PO4)0.2 + 4HCl Transistor behavior July 18, 2015 July 18, 2015 19 HP Confidential GSH, page 19 Rapid Low Temperature Reaction: ZnO Limitations of Past Approaches High processing temperatures, poor performance and non-ideal behavior caused by: • Residual spectator ions (Halides, Nitrates, Etc.) • Combustion products (Organics) • Grain boundaries • Film defects due to material loss July 18, 2015 July 18, 2015 20 HP Confidential GSH, page 20 Rapid Low Temperature Reaction: ZnO Precursor: ZnCl2(aq) + 2NH3(aq) +2H2O → Zn(OH)2(s) + 2NH4Cl(aq) Centrifuge and Rinse Zn(OH)2(s) + xNH3(aq) ↔ Zn(OH)2(NH3)x(aq) Conversion Zn(OH)2(NH3)x(aq) → ZnO(s) + xNH3(g) + H2O(g) 300º C pH -1 1 July 18, 2015 July 18, 2015 3 Zn+ (aq) 5 7 9 11 Zn(OH)2(s) HP Confidential 13 15 -2 Zn(OH)4 (aq) 21 GSH, page 21 Rapid Low Temperature Reaction: ZnO Results •Polycrystalline ZnO films Rms Roughness ~ 45Å (25μm2) • Transistor behavior ≤ 300°C • Mild deposition conditions • Direct deposition of metal oxo-hydroxide •Low mobility/current density July 18, 2015 July 18, 2015 22 HP Confidential GSH, page 22 Rapid Low Temperature Reaction: Aluminum Oxide Phosphate (AlOP) Al2O3 Corundum July 18, 2015 July 18, 2015 AlPO4 Berlinite HP Confidential 23 GSH, page 23 Rapid Low Temperature Reaction: (AlOP) Precursor Al(OH)3(s) + 2HCl(aq) +½H3PO4(aq) 95º C Al(OH)Cl2(aq) + ½H3PO4(aq) +2H2O Polymerization Al(OH)Cl2(aq) + ½H3PO4(aq) 275º C AlO3/4(PO4)1/2(s) + 2HCl (g) + ¼H2O July 18, 2015 July 18, 2015 24 HP Confidential GSH, page 24 Rapid Low Temperature Reaction: (AlOP) Results • Amorphous AlO3/4(PO4)1/2 dielectric films • Rms roughness 2.2Å (25 μm2) • Low temperature dehydration (275º C) • Highly uniform dielectric properties • Mechanically robust films • Deposition pH 3-4 July 18, 2015 July 18, 2015 25 HP Confidential GSH, page 25 Rapid Low Temperature Reactions: Chemical Implications •Aluminum Oxide Phosphate: Widely applicable chemistry - Building a “Tool Box” •Tin Oxide Phosphate: Seeking intelligent deposition routes •Zinc Oxide: Direct chemical deposition of the desired material •Hafsox/La: Functional gate dielectric Entirely Solution Processed Devices July 18, 2015 July 18, 2015 26 HP Confidential GSH, page 26 Device Characterization • Parallel-Plate Capacitor or MIM (Metal Insulator Metal) – Device Structure • Insulator material between two metal plates – MIM Characterization • Loss Tangent • Permittivity • Breakdown Strength July 18, 2015 July 18, 2015 27 HP Confidential GSH, page 27 Dielectric Performance Material ATO SiO2 Hafsox (Thermal) Aluminum Oxide Phosphate Loss Tangent at 1kHz (%) 1.36 <0.01 0.30-0.50 1.20 Permittivity @ 1kHz 16.25 3.9 9-12 4.30 Breakdown Strength (MV/cm) 4.26 8.5 Sample Size – Hafsox 4-5 References – • 36 substrates, 216 devices – Aluminum Oxide Phosphate ATO • Jeff Bender – • 1 substrate, 6 devices July 18, 2015 July 18, 2015 4.94 SiO2 • Handbook of Thin Film Technology HP Confidential 28 GSH, page 28 Device Characterization • Thin Film Transistor – Device Structure • Bottom-Gate Physical vapor deposition Solution based deposition July 18, 2015 July 18, 2015 Substrate provided by HP HP Confidential 29 GSH, page 29 Device Characterization • Thin Film Transistor Characterization – ID-VDS • DC • Qualitative Characteristics • Current Drive – ID-VGS • DC • Mobility (VDS = small, typically 1 V) • Von – Depletion vs. Enhancement Mode • On-to-off Ratio (VDS = large, typically 30 V) – Device Geometry – Gate Leakage July 18, 2015 July 18, 2015 30 HP Confidential GSH, page 30 Solution Deposited Thin Films Device Type Motivation PVD zinc tin oxideHafsox Show feasibility of Hafsox as gate insulator Tin oxide phosphate Solution based channel deposition Zinc oxide Solution based channel deposition Zinc oxide-Hafsox Low temperature integration of solution processed channel and gate insulator July 18, 2015 July 18, 2015 31 HP Confidential GSH, page 31 Sputtered ZTO on Hafsox -Annealed at 300 ˚C Annealed at 300 °C μinc=6.5 μavg=4.7 VGS = 0 to 10 V in 1V Steps July 18, 2015 July 18, 2015 32 HP Confidential GSH, page 32 Solution Deposited Thin Films Device Type Motivation PVD zinc tin oxideHafsox Show feasibility of Hafsox as gate insulator Tin oxide phosphate Solution based channel deposition Zinc oxide Solution based channel deposition Zinc oxide-Hafsox Low temperature integration of solution processed channel and gate insulator July 18, 2015 July 18, 2015 33 HP Confidential GSH, page 33 Spin-Coated Tin Oxide Phosphate Annealed at 500 °C VGS = 0 to 40 V in 5V Steps Max VON = -7V Current Drive of 225nA July 18, 2015 July 18, 2015 On-to-Off ~104 34 HP Confidential GSH, page 34 Solution Deposited Thin Films Device Type Motivation PVD zinc tin oxideHafsox Show feasibility of Hafsox as gate insulator Tin oxide phosphate Solution based channel deposition Zinc oxide Solution based channel deposition Zinc oxide-Hafsox Low temperature integration of solution processed channel and gate insulator July 18, 2015 July 18, 2015 35 HP Confidential GSH, page 35 Spin-Coated Zinc Oxide on SiO2 Annealed at 600 °C Max Current Drive of 37μA VGS = 0 to 40 V in 5V Steps July 18, 2015 July 18, 2015 36 HP Confidential GSH, page 36 Solution Deposited Thin Films Device Type Motivation PVD zinc tin oxideHafsox Show feasibility of Hafsox as gate insulator Tin oxide phosphate Solution based channel deposition Zinc oxide Solution based channel deposition Zinc oxide-Hafsox Low temperature integration of solution processed channel and gate insulator July 18, 2015 July 18, 2015 37 HP Confidential GSH, page 37 Spin-Coated Zinc Oxide on Hafsox Annealed at 300 °C Max Current Drive of 1μA VGS = 0 to 40 V in 5V Steps VON = -24V July 18, 2015 July 18, 2015 On-to-Off ~104 38 HP Confidential GSH, page 38 Inkjet Deposition Yu-Jen Chang Outline Semiconductor Material – Zinc Indium Oxide (ZIO) Previous work Channel layer patterning Device fabrication and characterization Precursor solution study Dielectric Material - Hafsox Precursor solution Device fabrication and characterization Summary and ongoing work July 18, 2015 July 18, 2015 40 HP Confidential GSH, page 40 Zinc Indium Oxide (ZIO) Previous work Spin coating Indium and zinc chlorides were combined with gluconic acid to form the aqueous precursor solution. The precursor was spin-coated and heated at 130ºC. Additional heating was employed at temperatures in the range 300-575ºC. The depletion –mode ZIO transistor had shown an incremental mobility of ~ 0.05 cm2/V-sec at Vgs = 20 V. Von ~ -20 V and an on-to-off ratio of approximately 103. July 18, 2015 July 18, 2015 41 HP Confidential GSH, page 41 Zinc Indium Oxide (ZIO) Previous work Inkjet printing ZIO thin films using diluted stock solution were prepared via inkjet printing. Bottom gate ZIO MISFETs on oxidized silicon coupons were fabricated with different post annealing temperature ranging from 300 to 600oC. Light source was employed to stabilize the thin film and overcome the de-wetting problem. No gate-modulated transistor behavior were obtained for Inkjet printed ZIO TFT devices. July 18, 2015 July 18, 2015 42 HP Confidential GSH, page 42 Zinc Indium Oxide (ZIO) Inkjet printing Growth Mechanism Metal halide precursor solution Inkjet printing O2 source +H2O Acetonitrile Evaporation Post annealing Desorption Liquid thin film Metal oxide Si coupon substrate Si coupon substrate July 18, 2015 July 18, 2015 HCl 43 HP Confidential GSH, page 43 Zinc Indium Oxide (ZIO) Inkjet printing An alternative ink solution was prepared by dissolving 0.015M of ZnCl2 and 0.015M of InCl3 in 25ml acetonitrile at room temperature. First pass bottom gate ZIO MISFET was fabricated. Gate-modulated transistor behavior was obtained but large gate leakage currents were found. To avoid this problem is to pattern the semiconductor channel layer July 18, 2015 July 18, 2015 44 HP Confidential GSH, page 44 Zinc Indium Oxide (ZIO) Channel layer patterning ~12 mm Inkjet Printing 3 Device S/D contacts 10 Characterization 15 mm Stripe patterned ZIO thin films were thermal ink-jetted on Si/SiO2 test coupon to fabricate ZIO TFTs. Gate leakage current was significantly reduced by 2 to 3 orders of magnitude for stripe patterned (~3mm x12mm) ZIO TFTs (1e-10~1e-13 Amp at Vg=0V) comparing to non-stripe patterned ones. July 18, 2015 July 18, 2015 45 HP Confidential GSH, page 45 Zinc Indium Oxide (ZIO) Device fabrication and characterization ZnCl2 and InCl3 were dissolved in 25 ml of acetonitrile with a molar ratio of 1 to 1 (0.015M) as precursor solution for ink jet printing. The modified HP 1220C inkjet printer was used to print the thin ZIO layer. Working ZIO TFTs were obtained from films annealed at 325oC, 400oC, 600oC, and 800oC (in acetonitrile); 375oC (in ethanol) July 18, 2015 July 18, 2015 46 HP Confidential GSH, page 46 Zinc Indium Oxide ID-VDS Characteristic (600 ºC, Acetonitrile) 2.0E-05 2.5E-06 W/L = 7 L = 200 um ID (A) 1.5E-06 1.0E-05 1.0E-06 5.0E-06 IG(A) 2.0E-06 1.5E-05 5.0E-07 0.0E+00 0.0E+00 0 10 20 30 VDS (V) • I-V characteristics for inkjet ZIO TFTs annealed at 600 ºC for 1 hour using acetonitrile as the precursor solvent. • 2015 W/L=7 and µinc ~0.7 cm2/V-s. July 18, July 18, 2015 HP Confidential 47 GSH, page 47 Zinc Indium Oxide ID-VDS Characteristic (800 ºC, Acetonitrile) 1.E-09 6.E-07 W/L = 7 L = 200 um 1.E-09 4.E-07 8.E-10 3.E-07 6.E-10 2.E-07 4.E-10 1.E-07 2.E-10 0.E+00 0.E+00 0 20 10 IG(A) ID (A) 5.E-07 30 VDS (V) • I-V characteristics for inkjet ZIO TFTs annealed at 800 ºC for 1 hour using acetonitrile as the precursor solvent. • 2015 W/L=7 and µinc ~0.013 cm2/V-s. July 18, July 18, 2015 HP Confidential 48 GSH, page 48 Zinc Indium Oxide ID-VDS Characteristic (375 ºC, Ethanol) 8.E-09 7.E-09 W/L = 7 L = 200 um 6.E-08 6.E-09 5.E-09 4.E-09 3.E-09 ID (A) 5.E-08 4.E-08 3.E-08 2.E-08 IG(A) 7.E-08 2.E-09 1.E-09 0.E+00 1.E-08 0.E+00 0 10 20 30 VDS (V) • I-V characteristics for inkjet ZIO TFTs annealed at 375 ºC for 1 hour using ethanol as the precursor solvent. • 2015 W/L=7 and µinc ~0.005 cm2/V-s. July 18, July 18, 2015 HP Confidential 49 GSH, page 49 Zinc Indium Oxide (ZIO) SEM analysis on a working TFT using inkjet ZIO thin film The top view image of the gate region The cross-sectional view of the gate region, the thickness of ZIO thin film is ~10 to 15nm. July 18, 2015 July 18, 2015 The top view image of the region outside the device gate 50 HP Confidential GSH, page 50 Zinc Indium Oxide (ZIO) (a) AMD cleaning Precursor solution study Precursor solutions listed in Table were inkjet printed on Si/SiO2 test coupon for film formation and patterning study. Solvents Film Quality (b) AMD cleaning Water/Acetonitrile Poor (10 to 90% of water) Dewetting Isolated dots Water/Ethanol (10 to 90 % of water) Acetonitrile Fair Dots on the surface Fine Tiny Dots on the surface Ethanol July 18, 2015 July 18, 2015 Patterning No pattern Fine Solution spread out No pattern 51 HP Confidential GSH, page 51 Zinc Indium Oxide (ZIO) Precursor solution study Volumetric ratios for Ethanol/Acetonitrile 5/95% 14.66o 10/90% 25/75% 10.27o <10o Increasing contact angle July 18, 2015 July 18, 2015 50/50% 75/25% <10o <10o Not much different by changing Ethanol/Acetonitrile volumetric ratio HP Confidential 52 GSH, page 52 Zinc Indium Oxide (ZIO) Summary Processing Method Spin coating Inkjet printing Patterning Non-available Available Device Type Depletion-Mode Enhancement-Mode Device Performance µinc ~0.05 cm2 V-1 s-1 µinc ~0.7 cm2 V-1 s-1 Ongoing work Solvent Thickness Morphology Zn/In ratio July 18, 2015 July 18, 2015 53 HP Confidential GSH, page 53 Hafnium Oxide Sulfate (Hafsox) Precursor solution ,Device fabrication and characterization HfOCl2 ,,La2(SO4)3 ,H2SO4 and DI water was used for preparing the Hafsox precursor solution for spin coating process. Diluted precursor solution suitable for inkjet printing process was prepared by 0.01M HfOCl2 and 0.002M H2SO4 in solution of water/ethanol (ethanol is 10% of the solution volume). Single layer and multilayer deposition were performed through inkjet printing process for depositing Hafsox thin film. Hafsox thin film deposition via inkjet printing on Tantalum surface was performed and device was tested by MIM 54 July 18, 2015 capacitor structure. July 18, 2015 HP Confidential GSH, page 54 Hafnium Oxide Sulfate (Hafsox) Scanning Electron Microscopy (SEM) characterization Defects and pinholes were observed in SEM micrograph July 18, 2015 July 18, 2015 55 HP Confidential GSH, page 55 Hafnium Oxide Sulfate (Hafsox) Pen autopsy images of a used inkjet cartridge after printing Hafsox precursor solution Completely closed nozzle with precipitate July 18, 2015 July 18, 2015 Resistor surface with precipitate Partially closed nozzle with precipitate HP Confidential 56 GSH, page 56 Hafnium Oxide Sulfate (Hafsox) Summary Inkjet printed Hafsox dielectric layer could not pass the MIM test for our study. SEM measurements indicated pin holes and defects on inkjet printed Hafsox thin films. Hafsox precursor solution had damaged and blocked the inkjet cartridge nozzles via precipitate around the nozzle opening and the resistors. This Hafsox precursor solution is not compatible with current inkjet printing system. July 18, 2015 July 18, 2015 57 HP Confidential GSH, page 57 4/5/2005 Material Exploration Hai Chiang Jason Stowers Amorphous Oxide Semiconductors • n-type amorphous oxide semiconductors – Composed of heavy-metal cation(s) with (n-1)d10ns0 (n≥4) electronic configuration • conduction band primarily derived of spherical s orbitals • cation examples include In, Zn, Sn, Ga, Cd, etc. • material example: indium oxide doped with tin (ITO)1 – Methods employed in exploration: • rf sputtering from ceramic targets • shadow mask pattering • bottom-gate structures fabricated on oxide Si coupons. 1. Y. Shigesato and D. C. Paine, Appl. Phys. Lett. 62, 1268 (1993) July 18, 2015 July 18, 2015 59 HP Confidential GSH, page 59 Inorganic Devices via Additive Processing Future Work: • Continue efforts on development of oxide electronics • expand learnings on device performance of solution processed vs. physical processed devices • demonstrate high mobility p-type behavior • demonstrate dielectric permittivity ~ 50 • demonstrate transistor channel mobilites ~ 50 • Extend program to include nonoxide channel materials • initial efforts on crystalline and amorphous tellurides • demonstrate transistor channel mobilities ~ 100 60 Previously explored materials: Zinc tin (indium) oxide Temp (C) Zinc tin oxide (1:1 mol)1,2 Zinc indium oxide (2:1 mol)2,3 inc (cm2/V-s) Von (V) inc (cm2/V-s) Von (V) RT - - 0.4 10 200 <0.01 25 2 -2 400 16 0 40 -35 600 26 -1 28 -50 1. R. Hoffman, HP internal document, WKRP, Oct. 22, 2003 2. H. Chiang, J. Wager, R. Hoffman, et al., Appl. Phys. Lett. 86, 013503 (2005) 3. H. Chiang and R. Hoffman, HP internal document, WKRP, Aug. 19, 2004 July 18, 2015 4. N.Dehuff, E. Kettenring, D. Hong, et al., J. Appl. Phys. 97, 064505 (2005) July 18, 2015 HP Confidential 61 GSH, page 61 8.E-04 log (ID(A)) Increasing VGS ID (A) 6.E-04 4.E-04 2.E-04 0.E+00 0 10 20 30 0 -2 -4 -6 -8 -10 -12 0 -2 -4 -6 -8 -10 -12 W/L = 5 L = 200 µm VDS = 30 V -10 0 10 20 30 log (|IG|(A)) Indium gallium oxide (1:1 mol): DC Electrical Characteristics 40 VGS (V) VDS (V) VGS = 0 to 30 V in 10 V steps • Channel layer subjected to 600 ºC anneal. • ITO source/drain contacts. July 18, 2015 July 18, 2015 62 HP Confidential GSH, page 62 Indium gallium oxide (1:1 mol): Channel mobility characteristic W/L = 5 VDS = 1 V 15 µinc ~ 16 cm2/Vsec 2 inc (cm /V s) 20 10 5 0 -10 0 10 20 30 40 VGS (V) • Fairly ideal, increases then saturates. July 18, 2015 July 18, 2015 63 HP Confidential GSH, page 63 Indium gallium oxide (1:1 mol): Performance Temp (C) Zinc tin oxide (1: 1 mol) Zinc indium oxide (2:1 mol) Indium gallium oxide (1:1 mol) inc (cm2/V-s) Von (V) inc (cm2/V-s) Von (V) inc (cm2/V-s) Von (V) RT - - 0.4 10 - - 200 <0.01 25 2 -2 - - 400 16 0 40 -35 7 7 600 26 -1 28 -50 15 1 July 18, 2015 July 18, 2015 64 HP Confidential GSH, page 64 Conclusions and path forward Conclusions: • Indium gallium oxide with qualitatively ideal ID-VDS characteristics. • Channel mobility characteristics comparable to zinc tin oxide, but lower magnitude. • Additional process flexibility - indium gallium oxide etches in HCl. Path Forward: • Explore stoichiometric variations of indium gallium oxide – literature suggests that performance increases with indium concentration.1 • Optimize deposition parameters. 1. T. Minami, Y. Takeda, et al., JVST A, 15, 958 (1997). July 18, 2015 July 18, 2015 HP Confidential 65 GSH, page 65 P-Type Material Investigation • • • • Recent work in this group has found several n-type materials with an amorphous crystal structure. 1,2 We hope to use additional properties of amorphous structure as a route to forcing candidate materials toward p-type behavior. The materials will be deposited amorphously by using low substrate temps during e-beam deposition. Crystallization will be frustrated through addition of ~10 to 40% Zn, In, Sn or combination there of. 1. Dehuff, N. L.; Kettenring, E. S.; Hong, D.; Chiang, H. Q.; Wager, J. F.; Hoffman, R. L.; Park, C.-H.; Keszler, D. A.. Transparent thin-film transistors with zinc indium oxide channel layer. Journal of Applied Physics (2005), 97(6) 2. Chiang, H. Q.; Wager, J. F.; Hoffman, R. L.; Jeong, J.; Keszler, D. A.. High mobility transparent thin-film transistors with amorphous zinc tin oxide channel layer. Applied Physics Letters (2005), 86(1) July 18, 2015 July 18, 2015 66 HP Confidential GSH, page 66 Candidate materials; Bi2O3 and Sb2O3 • • Known Materials – ZnO, Zn2+; [Ar] 3d10 4s0 – Cu2O, Cu1+; [Ar] 3d10 4s0 n-type p-type Candidate materials – Bi2O3, Bi3+; [Xe] 5d10 6s2 – Sb2O3, Sb3+; [Kr] 4d10 5s2 p-type? p-type? July 18, 2015 July 18, 2015 67 HP Confidential GSH, page 67 Energy Band Levels in Bi2O3 and Sb2O3 July 18, 2015 July 18, 2015 68 HP Confidential GSH, page 68 Local metal atom coordination Distorted Octahedral Environment for Bi in Bi2O3, bond length ~2.1-~3 Ang Proposed regular Octahedral Environment for Bi in amorphous Bi2O3 , bond length 2.4 Ang July 18, 2015 July 18, 2015 69 HP Confidential GSH, page 69 Bi2O3 Band Structure 6P 2P 6S July 18, 2015 July 18, 2015 70 HP Confidential GSH, page 70 Progress To Date • • • Depositions are completed for compositional arrays with Bi2O3 and Sb2O3 Optical and electrical measurements are underway Crystallization temperature being determined July 18, 2015 July 18, 2015 71 HP Confidential GSH, page 71 Summary of Solution Deposited Film Strategies • Semiconductor films will be made more dense to achieve higher mobility. • Dielectric permittivity will be increased through a layering technique. • Buffer films will be employed to improve film interfaces. 72 Summary of solution deposited thin films • • • • • Modified Hafsox was demonstrated as a gate dielectric AlOPhos exhibited uniform MIM breakdown characteristics TOP by solution deposition was demonstrated as a channel layer ZnO by solution deposition was demonstrated as a channel layer Solution deposited channel and dielectric layers were integrated in transistor devices July 18, 2015 July 18, 2015 73 HP Confidential GSH, page 73 Backup Slides July 18, 2015 July 18, 2015 74 HP Confidential GSH, page 74 Zinc Indium Oxide (ZIO) 1.80E-06 1.60E-06 Vg = -20 Vg = -16 1.40E-06 Vg = -12 1.20E-06 Ids (A) Vg = -8 1.00E-06 Vg = -4 8.00E-07 Vg = 0 Vg = 4 6.00E-07 Vg = 8 4.00E-07 Vg = 12 2.00E-07 Vg = 16 Vg = 20 0.00E+00 -2.00E-07 0 5 10 15 20 25 30 35 40 Vds (V) Drain current – drain voltage characteristics for a spincoated ZIO transistor with a W/L ratio of 7 and 100 nm of thermal SiO2 as the gate dielectric. July 18, 2015 July 18, 2015 HP Confidential 75 GSH, page 75 Zinc Indium Oxide (ZIO) Precursor solution study Contact angle measurement 100%-acetonitrile 100%-Ethanol Θ Contact angle – 51o Contact angle - ~ 0o July 18, 2015 July 18, 2015 76 HP Confidential GSH, page 76 Hafnium Oxide Sulfate (Hafsox) Solubility of aqueous solution of HfOCl2 and H2SO4 0.1 total Sulfate (M) 0.08 0.06 0.04 0.02 0 0 July 18, 2015 July 18, 2015 0.02 0.04 total Hafnium (M) HP Confidential 0.06 0.08 77 GSH, page 77 Hafnium Oxide Sulfate (Hafsox) Atomic force microscopy (AFM) characterization The 2-D AFM micrograph and roughness analysis for a single coat Hafsox thin film with July ave.18,roughness ~0.688nm. 2015 July 18, 2015 The 3-D AFM micrograph for a single coat Hafsox thin film with thickness around 35nm. HP Confidential 78 GSH, page 78 Backup Slides: ZTO 700 ºC XRD Zn2SnO4 (311) 1000 Counts Zn2SnO4 (511) Zn2SnO4 (531) 500 Zn2SnO4 (220) Zn2SnO4 (222) Zn2SnO4 (533) 0 20 30 40 50 60 70 Position - 2 (°) July 18, 2015 July 18, 2015 79 HP Confidential GSH, page 79 Reference: Periodic Table July 18, 2015 July 18, 2015 80 HP Confidential GSH, page 80