不同磁控溅射方式制备的C掺杂h-BN薄膜微观结构与导电性研究
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摘要
采用中频双极脉冲(IFBP)和射频(RF)磁控溅射分别在(100)取向的单晶Si衬底上沉积C掺杂h-BN(h-BN:C)薄膜,随后在95%Ar+5%H_2混合气氛中进行700℃退火处理,对其结构、化学组成、元素的化学价态、表面形貌以及导电性进行了分析研究。结果表明:两种溅射方法均成功在Si基片上制备出致密连续的h-BN:C薄膜,其电阻率可低至2. 9×10~4～2. 5×10~5Ω·cm。对比发现两种制备方法中IFBP磁控溅射具有较快沉积速率,制备出的h-BN:C薄膜结构更稳定,结晶性更好;而RF磁控溅射制备的h-BN:C薄膜经700℃退火处理后形成了层状结构。在溅射气氛中掺入一定量H_2对提高h-BN:C薄膜稳定性极为重要,而沉积后的低温退火处理更可提高其结晶性和稳定性。
The C doped h-BN( h-BN:C) films were deposited on( 100) Silicon substrate through intermediate frequency bipolar pulsed( IFBP) and radio frequency( RF) magnetron sputtering methods at the ambient temperature,followed by annealing at 700 °C in a mixture of 95% argon and 5% hydrogen. The microstructure,elemental composition and chemical valence,surface morphology and conductivity of the h-BN:C films were studied. The results show that the h-BN:C films with compact and uniform grains are successfully prepared by both two methods,while their resistivity is decreased to about 2. 9 × 10~4～ 2. 5 × 10~5Ω· cm. It is found that the IFBP magnetron sputtering has faster deposition rate compared to RF magnetron sputtering,and the h-BN:C films prepared by this method possess good crystallinity and stability. After annealing at 700 ℃ for about 45 min,the morphology of the h-BN:C film prepared by RF magnetron sputtering is changed to layered structure. What's more,adding a certain amount of H_2 in the sputtering gas media is very important for improving the stability of the h-BN:C films. The crystallinity and stability of the films could be improved by annealing treatment with low temperature.
The C doped h-BN( h-BN:C) films were deposited on( 100) Silicon substrate through intermediate frequency bipolar pulsed( IFBP) and radio frequency( RF) magnetron sputtering methods at the ambient temperature,followed by annealing at 700 °C in a mixture of 95% argon and 5% hydrogen. The microstructure,elemental composition and chemical valence,surface morphology and conductivity of the h-BN:C films were studied. The results show that the h-BN:C films with compact and uniform grains are successfully prepared by both two methods,while their resistivity is decreased to about 2. 9 × 10~4～ 2. 5 × 10~5Ω· cm. It is found that the IFBP magnetron sputtering has faster deposition rate compared to RF magnetron sputtering,and the h-BN:C films prepared by this method possess good crystallinity and stability. After annealing at 700 ℃ for about 45 min,the morphology of the h-BN:C film prepared by RF magnetron sputtering is changed to layered structure. What's more,adding a certain amount of H_2 in the sputtering gas media is very important for improving the stability of the h-BN:C films. The crystallinity and stability of the films could be improved by annealing treatment with low temperature.
引文
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[34] Kim S Y,Park J,Choi H C,et al. X-ray Photoelectron Spectroscopy and First Principles Calculation of C Doped BN Nanotubes[J]. Journal of America Chemistry Society,2007,129(6):1705-1716.
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[36] Watanabe M O,Itoh S,Mizushima K,et al. Bonding Characterization of BC2N Thin Films[J]. Applied Physics Letters,1996,68(21):2962-2964.
[37] Mannan M A,Nahano M,Shigezumi K,et al. Characterization of Boron Carbonitride(C doped BN)Thin Films Deposited by Radiofrequency and Microwave Plasma Enhanced Chemical Vapor Deposition[J]. America Journal of Applied Physics,2007,5:736-741.
[38] Chien S C,Chattopadhyay S,Chen L C,et al. Mechanical Properties of Amorphous Boron Carbon Nitride Films Produced by Dual Gun Sputtering[J]. Diamond and Related Materials,2003,12(9):1463-1471.
[39] Husein I F,Zhou Y Z,Li F,et al. Synthesis of Carbon Nitride Thin Films by Vacuum Arcs[J]. Materials Science&Engineering A,1996,209(1-2):10-15.
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[41] He B,Chen G H,Li Z Z,et al. P-BN/N-Si Heterojunction Prepared by Beryllium Ion Implantation[J]. Chinese Physics Letters,2008,25(1):219-222.
[42] Guo N,Wei J,Jia Y,et al. Fabrication and Electrical Properties of Semi-Conductive h-BNCx Thin Films[J]. Science of Advanced Materials,2014,6(3):550-557.
[2] Izyumskaya N,Demchenko D O,Das S,et al. Recent Development of Boron Nitride towards Electronic Applications[J]. Advanced Electronic Materials,2017,3(5):1600485-1600490.
[3] Prakash A,Skaria G,Sundaram K B. Investigation on Electrical Properties of RF Sputtered Deposited BCN Thin Films[J]. Electrochemical Society,2013,4(5):25-29.
[4] Ying J,Zhang X W,Yin Z G,et al. Electrical Transport Properties of the Si-doped Cubic Boron Nitride Thin Films Prepared by In-Situ CoSputtering[J]. Journal of Applied Physics,2011,109(2):023716-023720.
[5] He B,Zhang W J,Yao Z Q,et al. P-type Conduction in Beryllium-Implanted Hexagonal Boron Bitride Films[J]. Applied Physics Letters,2009,95(25):252106-252108.
[6] Dahal R,Li J,Majety S,et al. Epitaxially Grown Semiconducting Hexagonal Boron Nitride as a Deep Ultraviolet Photonic Material[J]. Applied Physics Letters,2011,98(21):932-92.
[7] Kim S M,Hsu A,Min H P,et al. Synthesis of Large-Area Multilayer Hexagonal Boron Nitride for High Material Performance[J]. Nature Communications,2015,6(1):9662-9663.
[8] Reigada D C,Freire F L. Nitrogen Incorporation into Boron Carbide Films Deposited by DC-Magnetron Sputtering:Film Microstructure and Tribological Properties[J]. Surface&Coatings Technology,2001,142(144):889-893.
[9] Kosaka M,Urakami N,Hashimoto Y. Formation of Graphitic Carbon Nitride and Boron Carbon Nitride Film on Sapphire Substrate[J]. Japanese Journal of Applied Physics,2018,57(1):02CB09-1-02CB09-4.
[10] Smeets J,Van V,Bergh D,et al. Deposition of Wear-Resistant BN Coatings by r. f. Plasma-Assisted Chemical Vapour Deposition[J]. Thin Solid Films,1993,228(1-2):272-275.
[11] Lin J J,Roland Y T,Li H L,et al. Smoothening of Wrinkles in CVD-Grown Hexagonal Boron Nitride Films[J]. Nanoscale,2018,1(3):1-10.
[12] Wang H,Zhao C,Liu L,et al. Towards the Controlled CVD Growth of Graphitic B-C-N Atomic Layer Films:the Key Role of b-c Delivery Molecular Precursor[J]. Nano Research,2016,9(5):1221-1235.
[13]毕兆琪,张兵临,李运钧,等.氮化硼薄膜的脉冲激光沉积[J].中国激光,1999,22(1):65-68.
[14] Gago R,Jimenez I,Albella J M. Boron-Carbon-Nitrogen Compounds Grown by Ion Beam Assisted Evaporation[J]. Thin Solid Films,2000,373(1):277-281.
[15]杨大鹏,赵永年,李英爱,等.用射频磁控溅射法在c-BN晶体基底上生长c-BN薄膜[J].人工晶体学报,2006,35(5):953-957.
[16] Belkind A,Freilich A,Lopez J,et al. Characterization of Pulsed dc Magnetron Sputtering Plasmas[J]. New Journal of Physics,2005,7(1):90-91.
[17] Somkhunthot W,Burinprakhon T,Thomas I,et al. Bipolar Pulsed-dc Power Supply for Magnetron Sputtering and Thin Films Synthesis[J].Journal of Electrical Engineering,2007,9(2):20-26.
[18] Frach P,Gottfried C,Fietzke F,et al. High Power Density Pulse Magnetron Sputtering-Process and Film Properties[A]. 13th International Conference on Plasma Surface Engineering[C]. 2012:80-83.
[19] Wu B,Haehnlein I,Shchelkanov I,et al. Cu Films Prepared by Bipolar Pulsed High Power Impulse Magnetron Sputtering[J]. Vacuum,2018,207(17):216-221.
[20] Tsai T H,Yang T S,Cheng C L,et al. Synthesis and Properties of Boron Carbon Nitride(BN∶C)Films by Pulsed-DC Magnetron Sputtering[J]. Materials Chemistry&Physics,2001,72(2):264-268.
[21]龚甜,吴隽,李涛涛,等.负偏压对六方氮化硼薄膜沉积特性的影响[J].武汉科技大学学报,2015,38(5):351-356.
[22] Pokropivny V,Kovrygin S,Gubanov V,et al. Ab-Initio Calculation of Raman Spectra of Single-Walled BN Nanotubes[J]. Physica E,2008,40(1):2339-2342.
[23] Lee J S,Choi S H,Yun S J,et al. Wafer-Scale Single-Crystal Hexagonal Boron Nitride Film via Self-Collimated Grain Formation[J]. Science,2018,362:817-821.
[24] Quan H,Wang X,Zhang L,et al. Stability to Moisture of Hexagonal Boron Nitride Films Deposited on Silicon by RF Magnetron Sputtering[J].Thin Solid Films,2017,64(2):90-95.
[25] Nakao S,Sonoda T,Tsugawa K,et al. Effects of Nitrogen Gas Ratio on Composition and Microstructure of C Doped BN Films Prepared by RF Magnetron Sputtering[J]. Vacuum,2009,84:642-647.
[26] Prakash A,Sundaram K B. Optical and XPS Studies of C Doped BN Thin Films by Co-Sputtering of B4C and BN targets[J]. Applied Surface Science,2017,396:484-491.
[27] Dai X,Chen Y,Chen Z,et al. Controlled Surface Modification of Boron Nitride Nanotubes[J]. Nanotechnol. 2011,22(24):245301-245306.
[28] Pan W J,Sun J,Ling H,Xu N,et al. Preparation of Thin Films of Carbon-Based Compounds[J]. Applied Surface Science,2003,218(1-4):298-305.
[29] Gomezaleixandre C,Essafti A,Albella J M. Kinetic Study of the Diborane/Methylamine Reaction:Composition and Structure of c-b-n Films[J]. Journal of Physical Chemistry B,2000,104(18),4397-4402.
[30] Dinescu M,Perrone A,Caricato A P,et al. Boron Carbon Nitride Films Deposited by Sequential Pulses Laser Deposition[J]. Applied Surface Science,1998,s127-129(97):692-696.
[31] Perrone A,Caricato A P,Luches A,et al. Boron Carbonitride Films Deposited by Pulsed Laser Ablation[J]. Applied Surface Science,1998,133(4):239-242.
[32] Song L,Liu Z,Reddy A L M,et al. Binary and Ternary Atomic Layers Built from Carbon,Boron,and Nitrogen[J]. Advanced Materials,2012,24(36):4878-4895.
[33] Yang Q,Wang C B,Zhang S,et al. Effect of Nitrogen Pressure on Structure and Optical Properties of Pulsed Laser Deposited BCN Thin Films[J]. Surface&Coatings Technology,2010,204(11):1863-1867.
[34] Kim S Y,Park J,Choi H C,et al. X-ray Photoelectron Spectroscopy and First Principles Calculation of C Doped BN Nanotubes[J]. Journal of America Chemistry Society,2007,129(6):1705-1716.
[35] Zhou F,Adachi K,Kato K. Influence of Deposition Parameters on Surface Roughness and Mechanical Properties of Boron Carbon Nitride Coatings Synthesized by Ion Beam Assisted Deposition[J]. Thin Solid Films,2006,497(1-2):210-217.
[36] Watanabe M O,Itoh S,Mizushima K,et al. Bonding Characterization of BC2N Thin Films[J]. Applied Physics Letters,1996,68(21):2962-2964.
[37] Mannan M A,Nahano M,Shigezumi K,et al. Characterization of Boron Carbonitride(C doped BN)Thin Films Deposited by Radiofrequency and Microwave Plasma Enhanced Chemical Vapor Deposition[J]. America Journal of Applied Physics,2007,5:736-741.
[38] Chien S C,Chattopadhyay S,Chen L C,et al. Mechanical Properties of Amorphous Boron Carbon Nitride Films Produced by Dual Gun Sputtering[J]. Diamond and Related Materials,2003,12(9):1463-1471.
[39] Husein I F,Zhou Y Z,Li F,et al. Synthesis of Carbon Nitride Thin Films by Vacuum Arcs[J]. Materials Science&Engineering A,1996,209(1-2):10-15.
[40] Shishonok N A,Gatal’skii G V,Erosh A Y. Flow of Space-Charge-Limited Currents in Cubic Boron Nitride[J]. Crystallography Reports,2005,50(1):S58-S61.
[41] He B,Chen G H,Li Z Z,et al. P-BN/N-Si Heterojunction Prepared by Beryllium Ion Implantation[J]. Chinese Physics Letters,2008,25(1):219-222.
[42] Guo N,Wei J,Jia Y,et al. Fabrication and Electrical Properties of Semi-Conductive h-BNCx Thin Films[J]. Science of Advanced Materials,2014,6(3):550-557.