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Professor Zainal Abidin Talib Dr. Josephine Liew Ying Chyi

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1 UNDERSTANDING THE STRUCTURAL AND PHYSICAL BASIS OF SELENIUM BASED SEMICONDUCTOR
Professor Zainal Abidin Talib Dr. Josephine Liew Ying Chyi Professor W. Mahmood Mat Yunus

2 INTRODUCTION

3 Copper Selenide belongs to a family of chalcogenide materials
has received great attention due to its particular photoelectrical properties and wide applications in electronic and optoelectronic devices [1-12] such as: photodetector optical filter schottky-diodes thermoelectric converter solar cell

4 The attraction of this binary material also depends on its feasibility to use as a precursor material to incorporate indium or other elements made available and lead to formation of ternary compound such as copper indium diselenide (CuInSe2) or other multinary material for thin film solar cell application [13-17]. It has a wide range of stoichiometric compositions (CuSe, Cu2Se, Cu3Se2, Cu7Se4, Cu5Se4, CuSe2) and non-stoichiometric composition (Cu2-xSe) [8, 18] Copper selenide can be constructed into several well documented crystallographic (phases and structural) forms such as orthorhombic [17, 19-21], monoclinic [22], cubic [21-24], tetragonal [17, 21], hexagonal [24-26] etc depending on their compositions form by various preparation technique [22, 27].

5 Tin Selenide (SnSe) Tin Selenide is a p-type (IV-VI) semiconductor with attractive electronic and optical properties [1, 28-38] which bring numerous applications such as: Photovoltaic system Radiation detector Holographic recording systems Infrared optoelectronic devices Memory switching devices Lithium intercalation batteries Thermoelectric cooling

6 Tin Selenide are classified as narrow-gap semiconductors (bandgap 1 – 2 eV) and are capable of absorbing major part of solar energy for photovoltaic applications[1, 28, 39, 40]. Tin monoselenide is a p-type semiconductor with an orthorhombic structure. The tin(II) selenide crystals are construct by tightly bound layers which formed by double planes with zigzag chains of tin and selenium atoms[41]. The highly layered structure, typical of all orthorhombic chlacogenide crystals, causes a strong anisotropy of physical properties of tin(II) selenide. Because of their anisotropic character, the tin (II) selenide chalcogenides becomes an attractive layered compounds, and can be used as cathode materials in lithium intercalation batteries[42].

7 Copper Tin Selenide (Cu2SnSe3)
Ternary chalcogenide materials having a semiconductor nature are currently attracting the attention of investigators due to their outstanding optical-thermal-electrical-mechanical properties and wide variety of potential applications in the fields like [43 – 52]: Photovoltaic cell thermoelectric Heterojunction laser Non-linear optical material Electronics and optoelectronics devices

8 The study of these materials is important since their band gap and lattice parameters can be varied by changing the cation composition, low melting temperature at around 690oC, high mean atomic weight and high refractive indices [51, 53 – 55]. Copper indium diselenide (CuInSe2) currently is one of the main compound used in photovoltaic application. However, indium are not cheap, therefore replacing indium with tin will potentially be cost-competitive as tin supply are more abundant and cheaper. Preparation of copper tin selenide system will lead to lower production cost and making supply situation more stable.

9 NICKEL SELENIDE (NiSe)
Nickel Selenide , a p-type semiconductor with a band-gap of 620nm (2.0eV) reveals significant electronic and magnetic properties. NiSe is formed from Nickel and Selenium due to the valence electronic configuration of Ni (3d84s2) and the small difference in electronegativity between Ni (χ = 1.9) and Se (χ = 2.4)

10 IRON SELENIDE (FeSe2) Semiconductors
Potential material for future applications in magnetoelectronics Potential material for future applications in optoelectronic devices

11 ZINC SELENIDE (ZnSe) ZnSe is good candidates for applications in various optoelectronic devices such as light emitting diodes (LED), semiconductor laser and photodetector. This is because of the nanometer size structure makes the electronic energy state discrete. When the diameter of nanocrystals is decreased, the energy separation and quantum effect will be enhanced.

12 OBJECTIVE Fabrication of selenium based semiconductor (CuSe, SnSe, NiSe2, Cu2SnSe3) in powder form (compositional analysis) and thin film (deposition condition analysis). Optical, electrical and thermal properties characterization of the Se based semiconductor. Evaluate the temperature dependence of the selenium based semiconductor from the observation of structural, electrical, optical and thermal properties changes at various temperature.

13 IMPORTANT OF STUDIES It is evident that for the future well-being of nations, a supply of energy based on a renewable source which is economically and environmentally acceptable has to be developed. Successful production of an efficient metal chalcogenide solar cell and modules requires the coupling of fabrication techniques with a basic understanding of the devices. There is a need to develop a greater fundamental sciences and engineering basis for the selenium based semiconductor material devices and processing requirement. In this work, we have fill the information gap on literature about the fundamental study of the structural, electrical, thermal and optical studies in polycrystalline CuSe, SnSe, NiSe2, ZnSe, FeSe2 and Cu2SnSe3 material. This fundamental knowledge will guide us to find out the fabrication and design parameters, which are imposed by current technology, material specifications and irradiation conditions to maximize the solar cell efficiency.

14 Sample Preparation Powder preparation – Chemical Precipitation Technique Pellet preparation – Moulding Thin film preparation – Thermal Evaporation Technique

15 CuSe Powder Preparation
Chemical Precipitation Method Selenium alkaline aqueous solution (12 M NaOH g Se) (Solution A) Stirred for 2 hours Mixture stirred for 24 hours Black precipitate obtained Dried in oven ( 70oC) for 24 hr Structural studies by XRD Pressed into pellet CuCl22H2O solution (solution B) Centrifuge and wash in distill water

16 XRD pattern of CuSe Sample prepared at different Molarity of CuCl2.H2O
We found that by using the concentration of 0.03 mol CuCl22H2O, the CuSe powder with high purity has been successfully produced.

17 XRD Spectra of synthesized CuSe powder
All the peaks obtained are well matched with the JCPDS data (File No ) as Klockmannite, syn which belongs to the hexagonal system. Orientation along (102) plane was found to be most prominent.

18 EDX spectrum for synthesized CuSe powder
There are three prominent peaks corresponding to the Cu, Se and Au element. The Au signal detected in the EDX spectrum is the results of gold coating on sample to prevent charging. small signal of C and O observed is expected from the background environment and carbon tape holding the powder sample. There are no other impurities elements were found by EDX spectrum.

19 Synthesis SnSe Powder Chemical Precipitation Method
Selenium alkaline aqueous solution (0.56 mol NaOH g Se) (Solution A) (50 ml water) Stirred for 2 hours Tin (II) complex aqueous Solution (SnCl2 + 9 g tartaric acid) (solution B) Stirred for 2 hours Mixture stirred for 24 hours Black precipitate obtained wash in sequence using membrane filter centrifuge Dried in oven ( 70oC) Structural studies by XRD Moulding into pellet

20 XRD pattern of SnSe Sample prepared at different molarity of SnCl2

21 XRD Spectra of synthesized SnSe powder
All the peaks obtained are well matched with the JCPDS data (File No ) which belongs to the orthorhombic system. Orientation along (111) plane was found to be most prominent. The sharp peaks obtained indicate that the material produced is of high crystallinity.

22 EDX spectrum for synthesized SnSe powder
Strong peaks corresponding to Sn, Se and Au element are found in the spectrum, and no impurity peaks are detected in the EDX spectrum. The Au peak observed in the EDX spectrum is due to the gold sputtering coating on the sample to prevent charging while the carbon and oxygen peaks are due to the dissolved atmospheric CO2 or carbon tape holding the powder sample. The elemental analysis was carried out only for Sn and Se element and the average atomic percentage of Sn:Se is : in the ratio range 1.1 : 1 which is nearly stoichiometry and close to the expected value of 1:1 (SnSe) in agreement with the XRD data.

23 To study the effects of concentration NiCl2·6H2O in synthesizing NiSe
Mass of the Se powder was weighted Mass of NiCl2·6H2O was weighted Both mass were put together in a beaker Ethylenediamine were added into the beaker The solution were poured into the Teflon lined autoclave The autoclave were put into the oven for 180⁰C for 6 hours

24 XRD patterns of NiSe2 compound synthesized using different concentration of NiCl2·6H2O

25 XRD Spectra of synthesized NiSe2 powder
All the peaks obtained are well matched with the JCPDS data (File No ), Nickel (IV) Selenide which belongs to the cubic system. The sharp peaks obtained indicate that the material produced is of high crystallinity.

26 Synthesis of ZnSe Compound

27

28 XRD pattern of ZnSe synthesized with different ratio ZnCl2/Se

29 XRD Spectra of synthesized ZnSe powder
All the peaks obtained are well matched with the JCPDS data (File No ), stilleite which belongs to the cubic system. The sharp peaks obtained indicate that the material produced is of high crystallinity.

30 Synthesis of FeSe2 sample

31 40 ml of distilled water was prepared .
3 ml of N2H4•H2O was prepared. All the starting materials were added into distilled water and stir for 3 minutes at 6 rpm. Na2SeO3 and FeCl3•6H2O was prepared. The sample was transferred into 50 ml Stainless Teflon-lined autoclave and heated up at 140°C for 12 hours.

32 The sample was filtered with distilled water in a centrifuge for 15 times.
The sample was dry in an oven at 60°C for 48 hours. The sample was weight and transferred to a sample bottle. The sample was grind with pestle and mortar into powder form.

33 XRD patterns of FeSe2 compound synthesized using different concentration of NiCl2·6H2O
The FeSe2 peaks in the entire pattern obtained can be identified as orthorhombic FeSe2 with lattice constant a=4.80 Å, b=5.78 Å, c=3.58 Å, which matched the value in the standard data (ICSD, ). Other oxides formed are Fe3O4 (ICSD, ) and Fe2O3 (ICSD, ).

34 Schematic flow chart for the Cu2SnSe3 nanoparticles preparation
Chemical Precipitation Method selenium alkaline aqueous solution Se + NaOH to produce Se2- and ions Stirred for 2 hours Mixture stir for 24 hours precipitate obtained Dried in oven ( 70oC) for 24 hr Cu (II) tartrate complex solution (0.015, 0.030, 0.045, 0.060, 0.068, 0.075, 0.083, 0.090, and mol) CuCl2∙2H2O + tartaric acid Centrifuge and wash in distill water Tin (II) complex aqueous solution 0.078 mol SnCl2∙2H2O + tartaric acid Stirred for 2 hours pH control Grinding powder using mortar and pestle

35 XRD pattern of the copper tin selenide powder synthesized by controlling the concentration of copper chloride (CuCl22H2O) from to mol with the concentration of tin chloride (SnCl2∙2H2O) and Se fixed at and mol respectively The XRD results show that when excessive CuCl22H2O was added, the final product is a mixture of Cu3Se2, CuSe and Cu2SnSe3. Less CuCl22H2O concentration will lead to formation of SnSe and Cu2SnSe3 mixture. All these results indicate that the binary compounds such as CuSe and SnSe will become intermediates during the formation of product Cu2SnSe3. 0.068 mol CuCl2.2H2O concentration has been chosen as the optimum amount to further test on the pH condition

36 the growth solution of pH at 1
the growth solution of pH at 1.30 is the optimum acidity condition which favors the formation of Cu2SnSe3 phase without any other impurities. XRD pattern of copper tin selenide powder synthesized at different pH condition (pH 0.84, 1.09, , 1.65, 1.77, 1.90, 3.63, 6.51) with mol CuCl22H2O, 5.2 M SnCl2∙2H2O and 0.5 M Se concentration

37 XRD Spectra of synthesized Cu2SnSe3 powder
All the peaks obtained are well matched with the JCPDS data (File No ) as Copper Tin Selenide which belongs to the cubic system Orientation along (220) plane was found to be most prominent.

38 EDX spectrum of synthesized Cu2SnSe3 powder
The results show the prominent peaks in the EDX spectrum are attributed to Cu (34.54%), Sn (18.48%) and Se (46.97%). The Au signal detected in the EDX spectrum is the results of gold sputtering on powder sample to prevent charging while the carbon and oxygen signal are expected due to the dissolved atmospheric CO2 or carbon tape holding the powder samples. No other impurity elements are found in the EDX spectrum. The calculated average atomic ratio of Cu:Sn:Se appears to be nearly stoichiometric (2.1 : 1.1 : 2.9) which is close to the expected value of (2 : 1 : 3) the nominal composition of Cu2SnSe3 as suggested by the XRD study.

39 Methodology + Combination of evacuated quartz ampoule
Evacuated ampoule Combination of evacuated quartz ampoule & modified rocking furnace Evacuated ampoule + Source material ‘A furnace for producing chalcogenide based alloy and a method for producing thereof’ by Talib, Z. A., Sabli, N., Yunus, W. M. M., Shaari, A. H. (MyIPO Paten Pending: PI )

40 Results (Source Material)
Synthesized SnSe XRD pattern of synthesized SnSe powder (before deposition) Sabli, N., Talib, Z. A., Yunus, W. M. M., Zainal, Z., Hilal, H. S., and Fujii, M. (2014). SnSe thin film electrodes prepared by vacuum evaporation: Enhancement of photoelectrochemical efficiency by argon gas condensation method. Electrochemistry, 82(1), 1-6 Synthesized XRD data well matched with JCPDS data ( ) Powder can be used as source material for vacuum evaporation

41 Results (Source Material)
Synthesized Cu2SnSe3 XRD pattern of synthesized Cu2SnSe3 powder (before deposition) Synthesized XRD data well matched with JCPDS data ( ) Powder can be used as source material for vacuum evaporation

42 Results (Source Material)
Synthesized Cu2ZnSnSe4 XRD pattern of synthesized Cu2ZnSnSe4 powder (before deposition) Sabli, N., Talib, Z. A., Yunus, M., Mahmood, W., Zainal, Z., Hilal, H. S., and Fujii, M. (2013). CuZnSnSe Thin Film Electrodes Prepared by Vacuum Evaporation: Enhancement of Surface Morphology and Photoelectrochemical Characteristics by Argon Gas. In Materials Science Forum (Vol. 756, pp ). Synthesized XRD data well matched with JCPDS data ( ) Powder can be used as source material for vacuum evaporation

43 Mechanochemical solid state synthesis of Cd0.5Zn0.5Se
The starting materials were high-purity cadmium (99.99%), zinc (99.99%) and selenium (99.99%) elemental powders purchased from Alfa Aesar. Mixtures at the desired atomic ratios were placed in a stainless steel grinding jar with stainless balls under an inert atmosphere. The intensive grinding the mixtures was performed in a high-energy planetary ball mill PM 100 (Retsch) with a ball-to-powder ratio of 10:1. Grinding balls of 3 mm in diameter were used. The milling time was varied from 5 to 20 hours at a speed of 500 rpm. Small quantities of the as-milled powders were removed from the grinding jar at various time intervals for microstructural and optical characterization.

44

45

46

47 Pellet Sample Preparation
The synthesized CuSe and Cu2SnSe3 powders were weighed in the desired amount and then placed into the 8mm diameter mould to form a pellet shape sample by using a hydraulic press (SPECAC USA, model 15011) of 3 ton pressure. The pelletization process is to force the particles into close proximity. 38mm 30mm 4.5mm 5mm 6mm 8mm Pellet mould with 8 mm diameter

48 Thin Film Deposition Vacuum Chamber Pressure monitor AC Power Supply shutter substrate holder glass Sample to be deposited High vacuum created by diffusion pump backed by rotary pump Molybdenum/ tungsten filament Thermal Evaporation System (Edwards Auto 306 Vacuum Coating)

49 Methodology Install argon gas supply & nozzle to flow argon

50 Hypothesis 1 Hypothesis 2
After collision Cu (Atomic weight: ) Zn (Atomic weight : ) (3) Higher retained kinetic energy Sn and Se are expected to react Sn (Atomic weight : ) Se (Atomic weight : ) Ar ; inert gas After collision Propose: Argon gas injection system (2) Lighter atoms (Cu, Zn) have higher speed due to Ek = 1/2 mV2; Higher speed more collisions with Ar atoms lose kinetic energy Before collision (1) Compound (atoms/ions) heats at same temp; atoms have same mean kinetic energy (Ek = 3/2 kT) Higher argon gas volume Hypothesis 2 (Cu,Zn): SnSe Pure SnSe thin film More carriers e- e- e- CB CB Impurity level VB VB Compound Cu2ZnSnSe4: (25:12.5:12.5:50) Compound: SnSe (50:50)

51 Annealing process For the heat treatment process, the CuSe and Cu2SnSe3 film were placed on the quartz boat and heated with gas N2 (1cc/min) by using furnace. The annealing process was carried out at a temperature raised from room temperature 26 oC to 100 oC, 200 oC, 300 oC, 400 oC at an increasing rate (2 oC/min). Upon reaching the required temperature, it was maintained for 3 hours. The temperature was then natural cooling to room temperature for 24 hours.

52 Methodology

53 XRD (PanAnalytical X’pert PRO PW3040)

54 FESEM, EDX and TEM Field Emission Scanning Electron Microscope
(JOEL JSM-6700F) Transmission Electron Microscope (Hitachi H7100 TEM) Energy Dispersive X-Ray (EDX) (LEO 1455 VP SEM )

55 Schematic Diagram for Low Temperature Two Probe Measurement System
Liquid nitrogen Argon gas vacuum Temperature controller Argon gas Rotary pump Two probe system Voltmeter Current source Variable temperature optical cryostat

56 Schematic Diagram for Low Temperature Photoflash Technique
Liquid nitrogen Argon gas vacuum Temperature controller argon gas rotary pump Variable temperature optical cryostat Preamplifier Ref Signal Oscilloscope photodiode Camera flash Thermocouple sample

57 Laser flash NETZSCH (LFA 457) Microflash for high temperature thermal diffusivity measurement

58 Microstructure Analysis using AFM (Quesant Q-Scope 250)
The characterization of surface morphology of the CuSe thin films was studied by atomic force microscopy (AFM) technique (Quesant Q-Scope 250) in tapping mode at ambient temperature.

59 Ellipsometer Technique (ELX-02C)
Ellipsometer measures the change of polarization upon reflection or transmission. The ellipsometer mechanics consists of a transmitter unit (He-Ne laser – nm) and a receiver unit (polarising prism) fixed at the end of adjustable arms. Ellipsometry is an indirect method, i.e. in general the measured Ψ and Δ cannot be converted directly into the optical constants of the sample, a model analysis must be performed. Using an iterative procedure (least-squares minimization) unknown optical constants and/or thickness parameters are varied, and Ψ and Δ values are calculated using the Fresnel equations. The calculated Ψ and Δ values, which match the experimental data best, provide the optical constants and thickness parameters of the sample

60 Fiber Optic Spectrophotometer
The optical studies of CuSe film analyzed using Ocean Fiber Optics Spectrophotometer. The transmittance spectra in the region 300nnm – 800nm has been collected and optical parameters such as optical absorption coefficient and optical band gap has been evaluated.

61 X-Ray Powder Diffraction
Structural Analysis X-Ray Powder Diffraction

62 In-situ XRD pattern of synthesized CuSe powder at 100 – 300 K
The structure was stable at the temperature range 100K – 398 K where no additional or unassigned peaks are observed

63 In-situ XRD pattern of synthesized CuSe powder at 298 – 473 K.
At temperature started from 423 K, an additional peak is observed at 2 = 45.38 which corresponding to d-spacing value of 1.99 Å. This peak was identified to the standard pattern of stoichiometric Cu2Se called bellidoite (JCPDS ).

64 TGA and DTG curve for synthesized CuSe powder at heating rate 10 K/min
Phase transformation from CuSe to Cu2Se structure as the synthesized CuSe powder annealed at 653 K in N2 for 12 hours the decomposition behaviour is attributed to the formation of Cu2Se products due to the release of elemental Se.

65 In-Situ XRD pattern of synthesized SnSe Powder at 100 K – 300 K

66 In-Situ XRD pattern of synthesized SnSe Powder at 298 K – 473 K
The structure was stable from low temperature 100K until high temperature 473 K where no additional or unassigned peaks are observed. This indicates that the sample powder is stable and contains no impurities.

67 Annealing at 1173 K destroys the SnSe lattice (peaks of SnSe disappear in the sample) and leads to formation of SnO2 and Sn phases in the presence of oxygen and release of free selenium followed the reaction in eq. (5.9) [56, 57]: 2SnSe + 3O2 = SnO2 + Sn + 2SeO2 

68 In-Situ XRD pattern of synthesized Cu2SnSe3 Powder at 100 K – 300 K.

69 In-Situ XRD pattern of synthesized Cu2SnSe3 Powder at 298 K – 523 K.
The Cu2SnSe3 structure was very stable at the temperature range 100K – 523 K where no additional or unassigned peaks are observed

70 some additional characteristic peaks attributed to the Cu3Se2 (JCPDS: ), Cu2O (JCPDS: ) and Sn2O3 (JCPDS: ) phase are observed after the Cu2SnSe3 powder annealed at 773 K. Additional peaks present in Figure 5.35 are caused by the recrystallization and oxidation of the material at higher annealing temperature [58]. Comparison between the as-synthesized Cu2SnSe3 powder with the annealed Cu2SnSe3 powder

71 Morphology

72 SEM result for Synthesized CuSe powder
Fig (a-d) shows the SEM micrograph of the CuSe powder at ×, ×, × and 2500 magnification which showed particles rod-like shape. It is observed that the smallest grain size is of the order of 37 nm. The big islands are formed by the agglomeration of smaller grains with length in the range of nm. (a) (c) (b) (d)

73 Rod like shape particles
highest count of diameter size range in nm range average diameter size distribution of 54.1 nm FESEM image and particle size distribution histogram of synthesized CuSe powder. mean crystallite size obtained from XRD at temperature range of 100 – 473 K rod-like shape particles highest count of diameter size range in nm average size distribution of 35.2 nm. TEM image and particle size distribution histogram of synthesized CuSe powder

74 SEM result for Synthesized SnSe powder
SnSe powder showed particles with granules, sheet-like and agglomerate slightly. The SEM micrograph confirm the layered structure growth of the SnSe synthesis using chemical precipitation method. It is observed that the average grain size of the small spherical grains is  nm. (a) (c) (b) (d)

75 flake-like or plate-like structure is built up by the interconnected network or overlapping of nanorod of the SnSe particles which agglomerates together and link to layered semiconductor. the highest count of diameter size is in nm range average diameter size distribution of (50.6  1.2) nm. FESEM image and particle size distribution histogram of synthesized SnSe powder dispersion leads to the breakup of the flake-like or layered-like structure network into individual nanorod particles. highest count of particle size range in nm average size distribution of (48.5  2.8) nm TEM image and particle size distribution histogram of synthesized SnSe powder

76 SEM results for synthesized Cu2SnSe3 powder
Fig. (a-d) shows the SEM micrograph of the Cu2SnSe3 powder at ×, ×, × and 2500 magnification which show particles with granules like shape. It is observed that the average grain size of the small spherical grains is  36 nm. The grains are well defined, spherical, of almost similar size, which indicates that the powder produced from the precipitation technique was homogenous and uniform. (a) (c) (b) (d)

77 powder is homogeneous, spherical in shape and slightly agglomerate.
the highest count of diameter size range as (30 -40) nm average diameter size distributions as 36.3 nm. FESEM image and particle size distribution histogram of synthesized Cu2SnSe3 powder homogeneous distribution of the small spherical nanoparticles The highest count of diameter size range is obtained to be in between nm the average size distribution being of 23.0 nm. TEM image and (b) particle size distribution histogram of synthesized Cu2SnSe3 powder

78 Electrical Properties

79 Electrical conductivity as a function of temperature for CuSe in bulk form
the decrease of electrical conductivity can be explained by the reduction in Hall mobility, due to the influence of impurity, defect scattering, lattice scattering or surface scattering [10, 59 – 61]. the increase of the electrical conductivity with the temperature can be explained as a consequent of thermal activation of the electrons which gained enough energy to jump across the depletion layers at the crystallite boundaries which act as potential barriers for conduction electrons [62, 63]. reduction in Hall mobility due to phonon scattering variable range hopping thermionic emission

80 Hall mobility and carrier sheet densities as a function of temperature for CuSe in bulk form
The Hall mobility of the CuSe pellet decreases from (92.9  0.9) to (5.61  0.06) cm2/Vs as the temperature increased from 100 to 300 K The impurities or defects inside the polycrystalline compound will develop space charge polarization with the large concentration of the charge carrier and subsequently induced trapping or localization process which decrease the electrical conductivity [64]. the carrier sheet density of the CuSe pellet increase from (2.54  0.03)  1019 to (3.08  0.03)  1019 cm-2 with increasing temperature which corresponds to the behaviour normally observed in a non-degenerate semiconductor trend. This behaviour can be explained by the usual impurity concentration in which the excitation of conduction electrons occurs from impurity centres [65].

81 ln (T1/2) versus (1000/T) at 349- 449 K for CuSe in bulk form
Thermionic Emission The temperature dependence of the conductivity in the higher temperature range ( K) follows the thermionic emissions over the grain boundary potential model and obeys Seto’s [66, 67] extended version of the Petritz model using equation: The linearity of the plots reveals that thermally-assisted thermionic emission over the grain boundary potential contributes to the conduction mechanism and the grain boundary scattering of charge carriers is more predominant in the samples investigated. It is believed that the small value of activation energy in the this temperature region is the energy required to overcome the grain boundary potential in this polycrystalline materials ln (T1/2) versus (1000/T) at K for CuSe in bulk form

82 Variable Range Hopping
The hopping conduction mechanism should dominate at low temperatures since the electrons do not have sufficient energy to cross the potential barrier through thermionic emission. According to Mott, variable range hopping is expected to be predominant at the lowest temperature as electron can hops to the nearest neighbouring empty site or move to a more energetically similar remote site and leads to conductivity–temperature dependence follows equation [68, 69]: the linear variation observed between 99 – 214 K with a good fit to the conductivity–temperature data indicates that the possible conduction mechanism at these temperatures can be described by Mott’s [67, 70] variable range hopping law. ln (T1/2) versus (T-1/4) at K for CuSe in bulk form

83 variable range hopping
Electrical conductivity as a function of temperature for SnSe in bulk form The electrical conductivity is found to increase slowly in the temperature range 100 K-396 K followed by a drastically increase above 420 K. The nature of response exhibits the ordinary semiconducting behaviour of the material throughout the temperature range. The substantial increase in electrical conductivity of the SnSe pellet is mainly determined by the carrier sheet density of the sample which depict the carrier sheet density of the SnSe pellet follows an exponential temperature dependence of a typical semiconductors. variable range hopping thermionic emission

84 Hall mobility and carrier sheet densities as a function of temperature for SnSe in bulk form
the mobility decreases as the temperature increased from 100 to 300 K. In polycrystalline semiconductors the transport of carrier is driven by scattering mechanism at intercrystallite boundaries, rather than by intracrystallite characteristics. Based on the grain boundary trapping theory, the decrease of mobility and steep rise of the carrier is due to the total carrier depletion of the grains which able to capture and therefore immobilize free carriers [71, 72].

85 ln (T1/2) versus (1000/T) at 396- 526 K for SnSe in bulk form.
Thermionic Emission The variation of ln (T1/2) with inverse temperature is found to be fit linearly in the temperature range from 396 to 526 K for the SnSe pellet indicating that the conduction in this system is through the thermally assisted thermionic emissions over the grain boundary potential model [66, 67]. Conductivity in SnSe pellet increases exponentially with temperature indicating the heat induced energy which overcome the barrier at the grain boundaries within the sample. ln (T1/2) versus (1000/T) at K for SnSe in bulk form.

86 ln (T1/2) versus (T-1/4) at 113 – 243 K for SnSe in bulk form
Variable Range Hopping The linear dependence of the ln (T1/2) vs. T-1/4 can be interpreted as hopping transport phenomena. The possible conduction mechanism at these temperatures ranges may be due to a wide range of localization and variable range hopping conduction in the localized states [67, 70]. At lower temperature, the localized states conduction gradually becoming predominant due to the fact that the probably of thermal release of the carriers from the localized states near the mobility edge becomes rapidly smaller and charge carrier is more likely to hop to a neighbor site in the distribution [73]. ln (T1/2) versus (T-1/4) at 113 – 243 K for SnSe in bulk form

87 Electrical conductivity as a function of temperature for Cu2SnSe3 in bulk form
A decrease in conductivity observed for the Cu2SnSe3 pellet in region I (99 – 375 K) follow the Hall mobility results closely The increase of the electrical conductivity in region II indicates the carriers within these polycrystalline material obtain sufficient energy to cross the potential barriers at the grain boundaries. The increase of carrier sheet density resulted from the reduction of the intergrain barriers above 375 K also increase the conductivity [72]. reduction in Hall mobility due to phonon scattering variable range hopping thermionic emission

88 Hall mobility and carrier sheet densities as a function of temperature for Cu2SnSe3 in bulk form
The Hall mobility of the Cu2SnSe3 compound decreases as the temperature increases from 100 to 300 K attributed to the increased scattering due to the influence of impurity, defect scattering, lattice scattering, neutral or ionized impurity scattering and grain boundary scattering or surface scattering [10, 59 – 61, 74, 75]. The temperature dependence of Hall mobility fit the classical scattering mechanism at region I indicating that acoustic lattice scattering is a dominant effect in the carrier transport from 125 to 200 K. At region II, it is believed that the presence of grain boundaries in polycrystalline material explained according to Seto’s grain boundary trapping theory will affect the results of the temperature dependence mobility for Cu2SnSe3 pellet [66]. Region I Region II The carrier sheet density increases as the temperature increased from 100 to 300 K. At higher temperature (200 – 300 K), the increase of carrier sheet density can be explained by a usual impurity concentration in which the excitation of conduction electrons occurs from impurity centres [65]. Further temperature decrease down to 100 K leads to an exponential decrease of the carrier sheet density due to freezing of electrons to the shallow level impurities.

89 ln (T1/2) versus (1000/T) at 375- 523 K for Cu2SnSe3 in bulk form
Thermionic Emission the variation of conductivity as a function of temperature in higher temperature range (375 – 523 K) is explained by the polycrystalline nature of the Cu2SnSe3 pellet with existence of potential barriers at grain boundaries followed the model of thermionic emissions across grain boundary barrier conduction [66, 71, 76, 77]. The conductivity of these polycrystalline Cu2SnSe3 pellet depends sensitively on the grain boundaries such as the potential barriers and space charge region that are built up around them. ln (T1/2) versus (1000/T) at K for Cu2SnSe3 in bulk form

90 ln (T1/2) versus (T-1/4) at 148 – 328 K for Cu2SnSe3 in bulk form
Variable Range Hopping The ln (T1/2) vs. T-1/4 plots in Figure fit linear for the temperature range of ( K) which obeys the Mott’s T-1/4 law propose the occurrence of variable range hopping conduction as the most suitable conduction mechanism for explaining the conduction process in this temperature range. In the hopping conduction, electron can hops to the nearest neighbouring empty site or move to a more energetically similar remote site according to Mott [78]. ln (T1/2) versus (T-1/4) at 148 – 328 K for Cu2SnSe3 in bulk form

91 Thermal Properties

92 (intrinsic scattering) is dominant in 100 – 350 K
Thermal diffusivity and reciprocal thermal diffusivity measurement as a function of temperature on CuSe pellet Thermal diffusivity decreased from 1.20  10-2 to 6.01  10-3 cm2/s as temperature increased from 100 to 473 K. increase of phonon scattering (as phonons pass through the sample, they are scattered by the heavier atom which contributed by the carriers in the compound, grain boundaries as well as other phonons) decrease in the mobility of free charge carrier as shown in Hall mobility results Phonon scattering can be separate into temperature dependent intrinsic scattering factor and temperature independent extrinsic scattering factor lattice heat transfer (intrinsic scattering) is dominant in 100 – 350 K

93 lattice heat transfer may be dominant in this three temperature range
Thermal diffusivity and reciprocal thermal diffusivity measurement as a function of temperature on SnSe pellet thermal diffusivity results decrease from 3.80  to 1.60  cm2/s as the temperature increased from 100 to 523 K increase of phonon scattering (as phonons pass through the sample, they are scattered by the heavier atom which contributed by the carriers in the compound, grain boundaries as well as other phonons) decrease in the mobility of free charge carrier as shown in Hall mobility results (scattering process and phonon collisions decrease the mobility of charge carriers and subsequently decrease the thermal diffusivity) Phonon scattering can be separate into temperature dependent intrinsic scattering factor and temperature independent extrinsic scattering factor lattice heat transfer may be dominant in this three temperature range

94 lattice heat transfer may be dominant in this three temperature range
Thermal diffusivity and reciprocal thermal diffusivity measurement as a function of temperature on Cu2SnSe3 pellet the thermal diffusivity value decreases from 4.18  10-3 to 2.97  10-3 cm2/s when the temperature increased from 100 to 523 K. increase of phonon scattering (as phonons pass through the sample, they are scattered by the heavier atom which contributed by the carriers in the compound, grain boundaries as well as other phonons) decrease in the mobility of free charge carrier as shown in Hall mobility results (scattering process and phonon collisions decrease the mobility of charge carriers and subsequently decrease the thermal diffusivity) lattice heat transfer may be dominant in this three temperature range

95 Effect of annealing process
CuSe film

96 XRD pattern of CuSe film annealed at various temperature
Electrical Conductivity of CuSe film as a function of annealing temperature Optical band gap and refractive indices of CuSe film as a function of annealing temperature Formation of new phase (Cu2Se) Grain size increase (reduction of grain boundary scattering) Unsaturated defects in the localized state are gradually removed. The reduction number of unsaturated defects decreases the density of localized states in the band structure 373 K 473 K XRD pattern of CuSe film annealed at various temperature

97 Effect of annealing process
SnSe Thin Film

98 XRD pattern of SnSe films annealed at various temperature
Electrical Conductivity of SnSe film as a function of annealing temperature XRD pattern of SnSe films annealed at various temperature formation of new phase (SnO2) grain growth drastically decrease in grain size AFM images As-deposited 373 K 473 K 573 K 673 K

99 Optical band gap and refractive indices of SnSe film as a function of annealing temperature
Eopt for the annealed SnSe film is obtained based on the direct allowed transition mechanism. sharp change of Eopt may be connected to partial convertion of tin selenide film to tin oxide film This behaviour may be attributed to the removal of water vapour or defect level from the SnSe film after annealing process . During annealing, unsaturated defects in the localized state are gradually removed. The reduction number of unsaturated defects decreases the density of localized states in the band structure and consequently decreased the the nr

100 Effect of annealing process
Cu2SnSe3 Thin Film

101 XRD pattern of Cu2SnSe3 film annealed at various temperature
Electrical Conductivity of Cu2SnSe3 film as a function of annealing temperature XRD pattern of Cu2SnSe3 film annealed at various temperature increase in grain size improvement of crystallinity AFM images As-deposited 373 K 473 K 573 K 673 K

102 the change of the average grains into effectively larger grains
Optical band gap and refractive indices of Cu2SnSe3 film as a function of annealing temperature the change of the average grains into effectively larger grains During annealing, unsaturated defects in the localized state are gradually removed. The reduction number of unsaturated defects decreases the density of localized states in the band structure and consequently decreased the the nr The increase of surface roughness at the Cu2SnSe3 films interface contributed to the increased surface optical scattering and optical loss which might lead to decrease of the nr

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107 ACKNOWLEDGEMENTS The authors would like to thank the Ministry of Education and Universiti Putra Malaysia for their financial support through (FRGS ), (RUGS ) and (Geran Putra )

108 Thank you


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