1 Low temperature deposition of thin passivation layers by plasma ALD Bernd Gruska, SENTECH Instruments GmbH, Germany 1. SENTECH in brief 2. Low temperature deposition processes 3. SENTECH SI ALD LL System 4. Properties of ALD Al 2 O 3 films 5. Summary
2 SENTECH in brief Private company founded in 1990 Located in Berlin, Germany New building since 2010 60 employees ISO 9001 certificated Business fields Thin Film Metrology Metrology for PV Plasma Process Technology Atomic Layer Deposition
3 SENTECH in brief Located in Berlin-Adlershof, Germany s largest science and technology park WISTA-MG www.adlershof.de
SENTECH in brief Application experts at SENTECH Processing of customer samples Device demonstrations User training Application fields: R & D Quality control Photovoltaic Low damage etching Low temperature deposition Nano patterning Nano films 3D deposition www.sentech.de 4
5 Plasma Process Technology Plasma ALD Plasma deposition Cluster tool RIE, ICP-RIE PECVD, ICPECVD Cluster tools ALD / PEALD SENTECH laser end point monitor Endpoint monitor Plasma etching
6 Spectroscopic ellipsometers SENresearch for R&D and quality control Wide spectral range Highly flexible SE 850 DUV SENDURO 200/300 SENDIRA
Low temperature deposition processes Applications of low temperature deposition processes Passivation of organic materials (OLEDs) (T D 80 C) Isolation of interconnects on small gap compound semiconductors (T D 100-200 C) Passivation of pn-structures (mesas) of compound semiconductors (T D 200 C) www.sentech.de 7
Low temperature deposition processes Deposition methods Inductively coupled plasma enhanced chemical deposition (ICPECVD) Plasma enhanced atomic layer deposition (PEALD) www.sentech.de 8
Low temperature deposition processes ICPECVD SI 500 D ICP planar plasma source RT-400 C Gasses: SiH4, O2, NH3, N2, H2, CH4 Films :SiO2, SiNx, SiOxNy, a-si, SiC Growth rate: 30-50 nm/min Conformality:~0.7:1 Low ion energy, <10 ev www.sentech.de 9
Capacitance [F] compressiv - (10 8 Pa) - tensil Main properties of ICPECVD films 3 2 1 T = 130 C, n = 1.98-2.0 14 12 ICPECVD PECVD 0-1 Si-H Absorption /cm -1 10-2 -3 P ICP, flow 8-4 -5-6 NH 3 flow 6 4-7 -8 2-9 -10 2 4 6 8 10 12 14 16 0 50 100 150 200 250 300 350 p ( Pa ) Deposition temperature / C f=1mhz QSCV HFCV and QSCV ICPJ6 2.2E-10 2.1E-10 2E-10 1.9E-10 1.8E-10 1.7E-10 1.6E-10 1.5E-10 1.4E-10 1.3E-10 1.2E-10-10 -6-2 2 6 10 Bias Voltage [V] MOS barrier ICPECVD: SiO x, T= 260 C n B = 1.469 N ss = 0.2*10 11 cm -2 ev -1 E B = 8.6 MV/cm r = 1.1*10 18 Ohm cm www.sentech.de 10
11 Low temperature deposition processes Atomic Layer Deposition Complete control of deposition process in a nanometer scale Conformal coatings into high aspect ratio structures Pin-hole and particle free depositions Low temperature deposition by plasma enhanced ALD PEALD removes water as precursor Wide range of chemistry for film deposition
12 Atomic Layer Deposition of Al 2 O 3 ALD cycle using TMA and water vapor: 1) TMA chemisorption 2) Purging step 3) Water chemisorption 4) Purging step Applications: ALD Al 2 O 3 films have been investigated in different applications, such as: - Charge-recombination layers in solar cells [1] - Diffusion barriers in organic electronics [2] - Gate dielectrics in transistors [3, 4] - Passivation layers in Li-Ion batteries [5]
SENTECH SI ALD LL System Specifications Substrate size up to 8 Substrate temperature 400 (up to 600 C optional) Reactor wall temperature 150 C (optional 200 C) Precursor lines up to 4 separate inlets direct draw or bubble line 200 C heated heater jacket for container Gas lines up to 7 Plasma source true remote CCP source (option) In-situ diagnostic SENTECH ellipsometer QMS, QMC Options TMP with isolation valve Ozone line, Glove box Clusterable to other process modules www.sentech.de 13
14 SENTECH SI ALD LL System Systeme software - User-friendly, based on SENTECH plasma system software - Special tool for operating ALD-pulses - Reliable remote field controller (RFC) - Manual and automatic operation
15 SENTECH SI ALD LL System In-situ analysis Optional available: - Ellipsometry (laser, spectroscopic) - Mass Spectrometer (QMS) - Quartz Crystal Microbalance (QCM) Applications: Growth Satturation Resistivity Reation mechanismus Chamber conditions Precursor behavior LE, SE, QMC LE, SE, QMC SE QMC, QMS QMS QMS
16 SENTECH SI ALD LL System In-situ analysis by laser ellipsometry 25 / / 20 15 180 180 165 d = 0 nm calculated transients for n=1.45-1.85 measured transient / Al 2 O 3 thickness / nm 135 40 20 0 thickness / nm growth start 1000 2000 3000 4000 time / s / 150 135 120 105 90 d = 40 nm d Al2O3 = 0... 40 nm n Al2O3 = 1.64 = 65 T = 200 C n=1.55 n=1.65 n=1.45 75 n=1.85 n=1.75 60 15 20 25 30 35 40 45 /
17 SENTECH SI ALD LL System Key features of SI PEALD LL Flexible system architecture A wide range of processes and applications Thermal and plasma enhanced processing Plasma source can be separated from the system True remote plasma source Substrate outside of the plasma generation region In-situ diagnostic capability SENTECH ellipsometers, QMS Rugged design and small footprint System can be connected to cluster tool L x W x H: 1800 x 680 x 1840 mm²
18 Properties of ALD Al 2 O 3 films Thermal ALD on 8" Wafer, thickness and R.I uniformity Layer thickness Refractive index TMA + H 2 O: Layer thickness: 8" Wafer 49,9nm (± 1,2%) Sigma 0,283nm Growth rate 0,8 Å/cycle Substrate temperature 200 C n (@632,8 nm) 1,639 (± 0,15%) Cycle time 2 s
19 Properties of ALD Al 2 O 3 films Plasma enhanced ALD on 8" Wafer, thickness and R.I. uniformity Layer thickness Refractive index TMA + O 2 -Plasma: Layer thickness: 8" Wafer 26,8nm (± 1,6%) Sigma 0,232nm Growth rate 1,1 Å/cycle Substrate temperature 200 C n (@632,8 nm) 1,642 (± 0,58%) Cycle time 10,5 s
20 Properties of ALD Al 2 O 3 films Linearity of growth - Al 2 O 3 film thickness shows linear dependence on the number of cycles in ALD and PEALD. - PEALD provides a higher growth rate of 1.2 Å/cycle compared to ALD. The growth rate in ALD amounts 0.8 Å/cycle. Process parameter ALD PEALD Substrate temperature ( C) 200 200 Process pressure (Pa) 12 20 Plasma power (W) 0 100 Growth rate (Å/Cycle) 0.8 1.2 Cycle time (s) 4 8
21 Properties of ALD Al 2 O 3 films Conformality 18 nm ALD-Al 2 O 3 @ 80 C 21 nm PEALD-Al 2 O 3 @ 80 C 1) 3D resist structures were prepared on Si-Wafers* and coated with ALD and PEALD Al 2 O 3 at 80 C substrate temperature. 2) Prepared samples were treated with O 2 -plasma to remove resist and examined with REM*. Very good conformality to 3D structures *) Thanks to Dr. Hübner, IPHT-Jena, Germany, for preparing the 3D structures and doing the REM-measurement.
Depositionsrate [Å/cycle] www.sentech.de Refractive index n 22 Properties of ALD Al 2 O 3 films Low temperature deposition of Al 2 O 3 by PEALD 2.0 1.8 PEALD Al 2 O 3 PEALD Al 2 O 3 1.6 ALD Al 2 O 3 1.7 ALD Al 2 O 3 1.2 1.6 0.8 1.5 50 100 150 200 Substrate temperature [ C] 1.4 0 50 100 150 200 Substrate temperature [ C]
C/Al [a.u.] www.sentech.de Absorption index 23 Properties of ALD Al 2 O 3 films Chemical information 0.25 0.20 XPS Al-O 200 C IR spectroscopy IR ellipsometer SENDIRA 0.15 80 C 0.10 27 C 0.05 0.00 0 25 50 75 100 125 150 175 200 225 Substrate temperature [ C] Impurities, methyl groups Wavenumber / cm -1
24 Summary - Outstanding features of SI PEALD-systems: Flexible system configuration for a wide range of processes and applications True remote plasma CCP source In-situ control by ellipsometry Rugged design and small footprint - Process results: Thermal and plasma enhanced deposition: very good uniformity Thermal and plasma enhanced deposition: very good conformality Incorporation of methyl groups at low temperature depositions Outlook Process optimization based on IR ellipsometry, in-situ laser ellipsometry
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