M. A. Nitti, M. Colasuonno, E. Nappi, A. Valentini

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1 Performance Analysis of Poly- and Nano-Crystalline Diamond based Photocathodes M. A. Nitti, M. Colasuonno, E. Nappi, A. Valentini INFN - Sezione di Bari - Via Amendola 173, 7126 Bari (Italy) 6 th International Workshop on Ring Imaging Cherenkov Counters (RICH 27) Stazione Marittima, Trieste, Italy 15 2 October 27

2 Other Contributors Diamond growth: F. Bénédic - Laboratoire d Ingénierie i des Matériaux et des Hautes Pressions, UPR1311 CNRS, Universite Paris 13, 99 av. J. B. Clément, 9343 Villetaneuse, France Raman spectroscopy: G. Cicala - Istituto di Metodologie Inorganiche e dei Plasmi (IMIP-CNR) Sezione di Bari - Via Amendola 122/D, 7126 Bari, Italy - Surface hydrogenation treatment: E. Milani, G. Prestopino - Dipartimento di Ingegneria Meccanica, Università di Roma Tor Vergata, Via del Politecnico 1, 133 Roma, Italy - Surface morphology analysis: E. Fanizza - Dipartimento di Chimica, Università di Bari, Via Orabona 4, 7124 Bari, Italy - 2

3 Outline External Quantum Efficiency (QE) results, in the range nm, of Poly- and Nano-Crystalline Diamond (PCD and NCD) PCs Informations on the Surface Morphology, Bulk Structure and Crystallinity y of PCD and NCD films Photoemission Model Surface Hygrogenation Effects on the QE Ageing due to air exposure Concluding remarks 3

4 Wide Band Gap Why DIAMOND for UV Radiation detectors? Wide Radiation Transparency High Carriers Mobility (> 2 cm 2 V - 1 s - 1 for e - ) High Thermal Conductivity (2 Wcm - 1 K - C) High Radiation Hardness Surface activation by hydrogen (NEA) 4

5 Diamond Films DEPOSITION PARAMETERS Poly and nanocrystalline diamond films were prepared by MWPECVD, at the LIMHP (Laboratoire d Ingénierie des Materiaux et des Hautes Pressions) - CNRS-UPR- Paris. Substrates = square n-doped silicon (1) of approximately 1 cm 2, ultrasonically abraded during 1h in a diamond powder suspension (~ 4 μm grain size). Film Input Surface Total Gas Gas Ratio Diamond Microwave Thickness Pressure Deposition film Power Ar/H Temperature 2 /CH 4 (μm) (mbar) (W) (%) ( C) GNCD /3/1 PCD /98/2 NCD /3/1 5

6 Literature A.S. Tremsin, O.H.W. Siegmund Proceedings SPIE, vol San Diego, California (2) & Diamond & Related Materials 14 (25) External QE Comparison with Literature 1 Best photoemission and λ for the th graphitic nanocrystalline diamond film GNCD PCD NCD 1 1,1, λ λ = 15 nm QE(%) λ = 15 nm QE(%) = 7 6

7 RAMAN SPECTRA of the diamond film photocathodes GNCD NCD PCD Raman shift (cm -1 ) (N. Wada, et al., J.Non Cryst. Solids 35/36 (198) 543) The PCD film exhibits an intense and narrow diamond peak at 1332 cm -1, and a broad peak at 155 cm -1 sp 3 > sp 2 The NCD film exhibits typical peaks at: 114 and 147 cm -1 of transpolyacetylene, 135 and 158 cm -1 of graphite D and G bands 1332 cm -1 of broad diamond peak sp 3 < sp 2 The GNCD film presents the typical bulk structure t of agraphitic nanocrystalline sample, with peaks at 135 and 158 cm -1 of graphite D and G bands, and the low intensity diamond peak at 1332 cm -1 sp 3 «sp 2 7

8 Surface morphology & Quantum um Efficiency of GNCD and PCD PCs 3D AFM surface image and distribution of heights of 1 GNCD PCD GNCD PCD 1,1 PXL R =3.3nm R a =3.5 nm a h MAX = 15 nm PXL h MAX = 12 nm, λ (nm) The distribution of heights is centred at a value of about 15 nm for both samples Hi Height h/ /nm Height /nm Significant difference in their surface texture The QE is comparable, and the GNCD PC presents a higher λ th with respect to the PCD one 8

9 Surface morphology & Quantum Efficiency of GNCD and NCD PCs 3D AFM surface image and distribution of heights of 1 GNCD NCD 1 GNCD NCD,1, R a = 3.33 nm 8 R a = 26.4 nm λ (nm) The distribution of heights of the NCD is centred at smaller PXL 6 4 h MAX = 15 nm PX XL 6 4 h MAX = 9 nm value, about 9 nm, than that of the GNCD Height /nm Very similar morphology Height /nm The QE of the NCD results to be lower 9

10 Surface morphology & Quantum Efficiency of GNCD and SCD PCs 3D AFM surface image and distribution of heights of GNCD SCD 1 1 GNCD SCD,1, λ (nm) R a = 3.4 nm R a = 1.8 nm PXL h MAX = 15 nm h MAX = 5 λ = 15 nm SCD QE(%) = Height /nm lower than that of GNCD, PCD and NCD PCs Very different morphology 1

11 RICH 24 Photoemission model of CsI PCs grown with two different deposition techniques two completely different morphologies θ hv hv hv UV Photons Electron photoexcitement hv hv M. A. Nitti et al. regions NIM A 553 (25) FILM FILM SUBSTRATO SUBSTRATE SUBSTRATE (a) Film deposited by thermal evaporation (b) Film deposited by IBS 11

12 PHOTOEMISSION MODEL for Diamond Photocathodes Distribution of heights Film UV Photons Electron photoexcitement regions Film Substrate (a) Substrate (b) Diamond films which present: (a) a low distribution of heights a larger portion of the electron photoexcitement regions is far from the film surface; therefore, many photoelectrons have to travel a too long path before escaping (b) a high distribution of heights Lower QE most of the electron photo-excitement region is located near to the surface, and so many more photoelectrons can escape from the film Higher QE 12

13 Dependence of the QE on the distribution of heigths GNCD NCD PXL h MAX = 15 nm 8 GNCD λ th = 23 nm PXL h MAX = 9 nm Height /nm 6 PCD λ th = 195 nm NCD Height /nm 4 λ th = 189 nm SCD PXL PCD Height /nm 2 h MAX = 12 nm λ th = 189 nm h (nm) MAX MAX SCD h MAX = 5 nm 13

14 Crystalline structure (XRD) 2 Si GNCD 2 Si NCD (111) θ ( ) Si PCD (4) Si (442) θ ( ) 1 5 1, (111) (22) θ ( ) (4) 1,4 1 6 SCD 5 (111) θ ( ) High LOCAL crystalline quality , , , , θ ( ) 14

15 Hydrogenation effect on the QE QE 15 nm = 13 1 GNCD untreated GNCD HYDROGENATED 1 1 QE each λ,1, λ (nm) SURFACE effect reduction in the photoemission threshold ENERGY E th NEA properties 15

16 Sample stability against ageing due to air exposure QE Comparison between the RQE = after QE 24 h in humid air as deposited of: a CsI PC the hydrogenated GNCD PC,65,6,55 GNCD HYDROGENATED CsI,5,45 4,4 After 24h air exposure: RQE CsI < RQE hydrogenated GNCD, λ (nm) the hydrogenated GNCD PC is more stable than the CsI one 16

17 Repeated H 2 plasma treatments: effects on the QE 1 GNCD HYDROGENATED - fresh - GNCD HYDROGENATED - after 24h AIR exposure - GNCD RE-HYD RO GEN ATED 1 QE 15 nm = 18 1,1 QE 15 nm = 3 I HYDROGEN-treatment:, λ (nm) - photoemission each λ - reduction in the photoemission threshold energy E th (SURFACE effect) II HYDROGEN-treatment, after 24h AIR exposure: - complete recovery of the QE (%) and E th at the same values of the I HYDROGENATION 17

18 Concluding remarks NCD PCs, that generally show a lower QE with respect to PCD ones, enhance their photoemission if a graphitic component is present in the film Not closed dependence of QE and grain size A possible explanation for the observed higher QE has been described in the light of a photoemission model correlated to the distribution of heights QE of Diamond based PCs QE of CsI PCs The hydrogenated diamond PC evidences: - the enhancement of the photoemission with respect to the untreated sample, and the lowering of the photoemission energy threshold -a stability in air better than the CsI one - the recovery of the initial QE value after air exposure, if the H 2 plasma treatment is repeated multiple times 18

19 Outlook Work is in progress in order to: better understand the role of the graphite and crystalline defects contribution to the photoemission i study doped diamond film PCs implement an innovative diamond deposition technique, and a new surface treatment 19

20 Thank You for Your Kind Attention!!! Maria Angela Nitti - mariangela.nitti@ba.infn.it itti@b i it - 2

Supplementary data. Ricerche (CNR), Via Orabona, 4 70125 Bari, Italy. E-mail: cardone@ba.iccom.cnr.it; 10 mrcr01ch@uniba.it.

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