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ASIC Design using Organic Transistors Submitted in partial fulfillment of the requirements of the degree of Doctor of Philosophy by Ramesh Raju Navan (Roll No. 05407009) Supervisors: Prof. V. Ramgopal Rao Prof. M. Shojaei Baghini Department of Electrical Engineering INDIAN INSTITUTE OF TECHNOLOGY BOMBAY, MUMBAI (2012) i Abstract This report summarizes the fabrication, characterization, mobility enhancement and development of a novel device and circuit simulation technique for organic thin film transistors (OTFTs). In this work we have mainly studied solution processed poly (3hexylthiophene) (P3HT) and vacuum evaporated pentacene based p-type OTFTs. The first part of the work is focused on the mobility enhancement of OTFTs. Several methods of dielectric surface treatments were found favorable for organic layer and they were compared with each other. A novel procedure for octadecyltrichlorosilane (OTS) deposition was explored and verified experimentally to give improved mobility of pentacene OTFTs. OTS deposition on silicon dioxide and hafnium oxide were found to give better mobility compared to other methods tried. We also demonstrated mobility enhancement of P3HT ptype of organic transistors by dispersing Zinc Oxide (ZnO) nanostructures into it. A comparative picture is presented between these composite based and pristine P3HT transistors. Our results indicates more than 60% mobility enhancement in the composite transistors compared to pristine ones. However, there is still scope for further improvement in terms of better dispersion of ZnO nanostructures. Due to lack of compact models for OTFTs we have used alternate approaches to perform device and circuit simulations of OTFTs and they are discussed as second part of the work. One approach of circuit simulation of OTFTs was to extract equivalent SPICE (Simulation Program with Integrated Circuit Emphasis) parameters of OTFTs with the help of particle swarm optimization (PSO) algorithm. The extracted equivalent SPICE parameters are used as a device model for SPICE based circuit simulations. Another approach for OTFT device simulation was done by use of ISE-TCAD (Integrated Systems Engineering Technology Computer Aided Design) in it the device parameters for silicon were replaced by those of organic semiconductor. The results obtained from device simulation procedure were then used to generate the Look-up Tables (LUTs) of the organic devices. LUT of the OTFT can also be directly obtained from the experimental data. LUT generated is used as a model file in SEQUEL (Solver for circuit EQuations with User-defined ELements) for simulating circuits. Simulated results were verified experimentally. ii The third part deals with the fabrication and optimization of gate dielectrics. Here we have demonstrated organic field effect transistors (OFETs) with photo-patternable, solution processed, nanoparticle composite high-k gate dielectric layer. The dielectric layer consists of Barium Titanate (BT) nanoparticles dispersed in SU-8, which makes it possible to use solution-processable methods. The dielectric constant k of the nanoparticle composite films can be tuned over a wide range by varying the concentration of BT particles, which enables lower voltage operation possible with these composite gate dielectric films. OFETs with P3HT as the semiconducting layer have been demonstrated; it was found that the OFETs with the nanocomposite dielectric layer show a significant improvement in the drive current yet retaining the photopatternability, which is an advantage for circuit fabrication. The composite being a high-k enables low voltage operation (∼4 V) compared to pristine SU-8 as a gate dielectric operating at high voltages (∼40 V). Working organic transistors and inverters with a high-k nanocomposite dielectric layer (k > 13) with considerably lower leakage current have been demonstrated. In the last part, a new compact OTFT-based analog to digital converter (ADC) was designed and simulated using LUT based approach in SEQUEL circuit simulator. The LUT data was obtained from fabricated P3HT-based OTFTs with the developed high-k photopatternable gate dielectric layer. The LUT simulation approach was validated at the circuit level using the measurements taken on fabricated OTFT-based inverter. With the limitation in yield and stability of P3HT-based components circuit modules were designed with fewer transistors. Designing a differential architecture makes it less sensitive to variation of threshold voltage of input transistors. The proposed design and circuit simulation results show a great promise for simulation and complex designing approach advantageous for different organic electronic applications. Keywords - organic semiconductors, OTFT, pentacene, P3HT, HfOx, SAM, ZnO, OTFT circuit simulation, signal conditioning, analog to digital converter. iii Contents Abstract ii List of Figures vi List of Tables xii Abbreviation and Nomenclature xiii 1 Introduction 1.1 Organic Semiconducting Materials 1.2 Conduction Mechanisms 1.3 OTFT Device Structure and Model 1.4 Circuit Simulation of OTFTs 1.5 Overview of the Thesis 1 3 4 5 8 9 2 Organic Thin Film Transistors Performance Parameters 2.1 Introduction 2.2 Factors Affecting Mobility 2.2.1 Deposition Process 2.2.2 Temperature 2.2.3 Charge Trappings in Polymer 2.2.4 Influence of Structural Imperfections in Polymer 2.2.5 Surface Modification Technique - SAM 2.2.6 Mobility Enhancement of Pentacene OTFT using SAM 2.2.7 Mobility Enhancement of P3HT OTFT using ZnO Nanostructures 2.3 Controlling Threshold Voltage 2.3.1 Factors affecting Threshold Voltage 2.3.2 Metal Work Function Tuning 2.3.3 Double Gate Structures 2.3.4 Self Assembled Monolayer 2.3.5 Deliberate Interface Trap Creation 2.3.6 Threshold Voltage Tuning of Pentacene OTFTs using SAM 2.4 Conclusion 12 12 15 15 16 16 17 18 23 34 45 46 48 48 49 50 50 59 3 Fabrication and Simulation of P3HT and Pentacene OTFT and Circuits 3.1 Introduction 3.2 P3HT OTFT Devices and Inverters 3.2.1 Fabrication and Characterization 3.2.2 OTFT Simulation using SPICE 3.2.3 Results and Discussions 3.3 Pentacene OTFT Devices and Inverters 3.3.1 Fabrication and Characterization 60 60 61 61 65 65 66 66 iv 3.3.2 OTFT Simulation using LUT based Approach 3.3.3 Results and Discussions 3.4 Circuit Design Methodology 3.4.1 Circuit Design Problems with OTFT Technology 3.4.2 Bootstrap Inverter 3.4.3 Bootstrapped Circuit Simulation 3.4.4 Bootstrapped Circuit Fabrication 3.5 Conclusion 70 73 78 79 79 80 83 85 4 Optimization of the Gate Dielectric 4.1 Introduction 4.2 Fabrication Procedure 4.3 Characterization Results 4.3.1 Silicon Nitride as Gate Dielectric 4.3.2 Hafnium Oxide as Gate Dielectric 4.3.3 Stacked Hafnium Oxide/Silicon Dioxideas gate dielectric 4.3.4 PMMA as Gate Dielectric 4.4 A Novel High-k (k > 40) Gate Dielectric 4.4.1 Introduction 4.4.2 Experiment 4.4.3 Results and Discussion 4.5 Solution Processed Photopatternable High-k Nanocomposite Gate Dielectric 4.5.1 Introduction 4.5.2 Experiment 4.6 Conclusion 87 87 87 88 89 89 90 90 91 91 91 92 93 93 95 100 5 OTFT Circuit Design and Simulation for Signal Conditioning Application 5.1 Introduction 5.2 Signal Conditioning Circuit 5.2.1 LUT based Simulation of High-k OTFT Device and Inverter Circuit 5.2.2 Analog to Digital Converter Design 5.3 Conclusion 101 101 102 105 107 110 6 Summary and Future Work 111 References 115 List of Publications 126 v List of Figures 1.1 1.2 1.3 OTFT device configurations: (1) Bottom gate (a) Top-contact device (b) Bottom-contact device (2) Top-gate……………………………………............. Structure of an all polymer transistor where source, drain and gate were printed by inkjet technique, semiconducting and insulating layers were spin coated/inkjet printed………………………………………………..................... 6 6 General flow showing optimized device fabrication steps and OTFT circuit simulation approach…………………………………………………………….. 9 1.4 Illustration of the organization of the thesis……………………………............. 11 2.1 Typical electrical characteristic of a p-channel OTFT device: (a) Output curve and (b) transfer curve…………………………………………………………… 13 2.2 Relation between grain size and mobility…….………………………………… 18 2.3 Formation of SAM on SiO2…...………………………………………………... 19 2.4 Octadecyltrichlorosilane structure…………………………………………….... 20 2.5 Hexamethyldisilazane structure………………………………………………… 21 2.6 Porphine structure……….……………………………………………………… 21 2.7 5-(4-Hydroxyphenyl)-10, 15, 20-tri (p-tolyl) porphyrin………………………... 22 2.8 Surface characterization based on contact angle measurements………………... 23 2.9 Formation of hydroxyl phenyl porphyrin SAM on SiO2……………………….. 26 2.10 AFM surface images of (a) bare silicon dioxide (SiO2) surface (b) HMDS SAM on SiO2 (c) OTS SAM on SiO2 (d) Piranha + OTS SAM on SiO2………. 27 2.11 Top-contact bottom-gate OTFT structure………………………………………. 28 2.12 Comparison plots with and without SAM……………………………………… 29 2.13 Top-contact bottom-gate OTFT structure………………………………………. 31 2.14 Comparison plots with and without SAM……………………………………… 32 2.15 Schematic of all-p type organic inverter with enhancement mode driver (M1) and Load (M2) and inverter cross-sectional view………………………………. 33 vi 2.16 Inverter DC characteristics (VDD = 4 V) of organic inverter with and without OTS SAM on sputtered HfOx as gate dielectric and dimensions (W/L)M1= 24850 μm/50 μm and (W/L)M2 = 5050 μm/50 μm, respectively………………... 34 Vapor-Liquid-Solid apparatus used for the growth of zinc oxide nanostructures…………………………………………………………………... 36 Scanning electron micrographs of the wool-like structures grown in the high temperature zone in a Vapor Liquid-Solid (VLS) Process……………………... 36 Cross-sectional view of the P3HT/ZnO nanocomposite transistor considered in this work………………………………………………………………………... 38 Comparison of typical (a) output characteristics, gate voltage is different for each curve, varied from 0 V to -40 V in steps of -5 V (b) transfer characteristics, drain Voltage is -40 V of transistors based on pristine P3HT and ZnO/P3HT composite transistors…………………………………………... 38 (a) SEM and (b) TEM images of ZnO nanorods grown for 1.5 h by a simple one-step chemical approach. A SAED pattern of ZnO nanorods is shown as the insets of the TEM images….............................................................................. 40 (a) Cross-sectional view of the P3HT/ZnO nanocomposite based bottom contact organic field effect transistor. (b) Transfer (IDS-VGS) characteristics comparison for different concentration of ZnO nanorods in P3HT/ZnO nanocomposite where VGS is varied from +10 to -40 V & VDS = -40 V (c) Output (IDS-VDS) characteristics of pristine P3HT devices. Similarly (d) to (f) show the output characteristics for 0.5 mg, 1 mg & 1.5 mg ZnO nanorods dispersed in a 1.5 mg of P3HT in chloroform solution where V DS is varied from 0 to -40 V & VGS varied from 0 to -40 V in steps of -10 V, respectively (W/L = 24300 µm /65 µm)……………………………………………………... 42 Statistically analyzed mobility data of pure and P3HT/ZnO (different ZnO weight %) nanocomposite. The observed increase in mobility is mainly due to the reduction of traps in P3HT………………………………………………….. 43 2.24 SEM image of ZnO nanorods (sample (a), sample (b) and sample (c))………... 44 2.25 XRD patterns of ZnO nanorods (sample (a), sample (b) and sample (c))……… 44 2.26 Transfer (IDS-VGS) characteristics comparison for different aspect ratios of ZnO nanorods in P3HT/ZnO nanocomposite. Here, VGS is varied from +10 to -30 V & VDS = -30 V for aspect ratio of 15, 25 & 60 ZnO nanorods dispersed in a 1.5 mg of P3HT in chloroform solution, respectively (W/L = 24000 µm/50 µm)………………………………………………………………………............ 45 2.27 Threshold voltage dependence on polymer thickness [71]……………………... 46 2.28 Change in threshold voltage with temperature [30]…………………………….. 47 2.29 Drain current vs. gate voltage stress [30]……………………………………….. 47 2.17 2.18 2.19 2.20 2.21 2.22 2.23 vii 2.30 Device geometry of dual gate structure [72]……………………………………. 48 2.31 Threshold voltage vs. top-gate voltage [72]…………………………………… 48 2.32 Drain current vs. gate voltage curves with and without OTS treatments [73]….. 49 2.33 Threshold Voltage vs. exposure time of treatment [75]………………………... 50 2.34 AFM surface images (a) SiO2 (b) Porphyrin SAM on SiO2 [35]……………….. 52 2.35 UV-Vis spectrum of porphyrin in toluene and and SAM on SiO2 [35]………… 53 2.36 Structure of OFET with SAM layer…………………………………………….. 53 2.37 Log |IDS|-VGS curve for OFET with W = 4186 μm and L = 100 μm for oxide thickness of 100 nm ……………………………………………………………. 54 Log |IDS| vs. VGS plot for devices with Al2O3 as dielectric and W = 2000 µm and L = 150 µm…………………………………………………………………. 54 2.39 AFM images of (a) pentacene on Al2O3 and (b) pentacene on SAM on Al2O3… 57 2.40 Id-Vg characteristics of OFET with and without SAM (copper porphyrin)……. 58 2.41 FTIR results of samples before and after plasma exposure…………………….. 58 3.1 OTFT structure in Bottom Gate Bottom contact configuration with patterned gate (Al)…………………………………………………………………............ 61 Output (IDS-VDS), characteristics of a typical fabricated OTFT with HfOx as gate dielectric.…………………………………………………………………... 62 IDS-VGS (triangles) and IDS1/2 -VGS (solid line) plots of OTFT with HfOx gate dielectric (W/L = 15200 µm/20 µm)…………………………………………… 62 Schematic of all-p type organic inverter with enhancement mode driver (M1) and load (M2).…………………………………………………………………. 63 DC transfer characteristics of an organic inverter with (W /L)M1 = 8400 µm/100 µm and (W/L) M2 = 2150 µm/100 µm………………………………….. 64 Measured transient characteristics of organic inverter. The transient delays are estimated to be roughly 10 ms………………………………………………….. 64 3.7 Comparison of measured vs. simulated IDS − VDS characteristics OTFTs ……... 66 3.8 Cross-section of the patterned gate fabricated OTFT…………………………... 67 3.9 Patterened gate OTFT with sputtered-SiOx (60nm) as gate dielectric and patterned pentacene as semiconducting material. ….…………………………... 67 2.38 3.2 3.3 3.4 3.5 3.6 viii 3.10 Schematic of all-p type organic inverter with enhancement mode driver (M1) and load (M2) and inverter cross-sectional view…….………………………… 68 The measured DC and transient characteristics of an inverter with (W/L)M1 = 24850 μm/50 μm and (W/L)M2 = 3550 μm/50 μm.……………………………... 68 3.12 Output characteristics with sputtered-HfOx (45nm) as gate dielectric…………. 69 3.13 The measured DC and transient characteristics of an inverter with (W/L)M1= 24850 μm/50 μm and (W/L) M2 = 5050 μm/50 μm…………………………….. 69 Patterened gate OTFT with sputtered HfOX (65nm) as gate dielectric and patterned pentacene as semiconducting material with (W/L) = 24850 μm/50μm 70 The measured DC and transient characteristics of an inverter with (W/L) M1 = 24850 μm/50 μm and (W/L) M2= 5050 μm/50 μm……………………………… 70 Cross-section of a bottom contact OTFT device drawn in MDRAW (ISETCAD tool) (a) before meshing (b) after meshing of the device……………… 72 Measured vs. simulated ID − VD characteristics for OTFTs fabricated (data scaled to width W=1μm)…………………………………………………........... 74 (a) DC transfer characteristics and (b) transient response of the simulated all ptype enhancement mode organic inverter for VDD = 5 V. Inset shows the schematic of Inverter……. …………………………………………………… 75 (a) Two input NAND gate with only p-type transistors gate (b) simulated characteristics…………………………………………………………………… 76 (a) Two input NOR gate with only p-type transistors gate (b) simulated characteristics…………………………………………………………………… 76 3.21 Output characteristics of a 5-stage simulated ring oscillator…………………… 77 3.22 Measured vs. simulated output characteristics for OTFTs……………………... 77 3.23 (a) P-type OTFT inverter and (b) Transient response of the simulated p-type enhancement-mode organic inverter for VDD = 4 V……………………………. 78 3.24 Bootstrapped inverter.…………………………………………………………... 79 3.25 Comparison of measured vs. simulated IDS − VDS characteristics OTFTs (W/L = 500 μm/150 μm)…………………………………………………………........ 81 Shows the results of transient simulation of p-type based inverter circuit and ptype bootstrapped inverter……………………………………………………… 81 Shows the p-type based dynamic logic circuit (a) without and (b) with bootstrap technique……………………………………………………………... 82 3.11 3.14 3.15 3.16 3.17 3.18 3.19 3.20 3.26 3.27 ix 3.28 Plots for p-type dynamic logic inverter with and without bootstrapping………. 82 3.29 (a) The schematic of bootstrap inverter circuit, (b) SEM picture of fabricated bootstrap inverter. (c) DC transfer characteristics of a fabricated bootstrapped organic inverter. The sweep rate of the input for DC characteristics of inverter is 0.1 V/s. The dashed curve shows the output for a normal inverter with identical transistors, (d) The transient response of the normal inverter and (e) The transient response of the bootstrapped inverter [82]……………………….. 85 4.1 Bottom-gate top-contact OTFT using BDFO as gate dielectric………………... 91 4.2 Transistor characteristics (a) drain current (ID) versus drain-source voltage (VDS) (b) drain current (IDS) versus gate voltage (VGS) of the OTFT with BDFO as the gate dielectric…………………………………………………………….. 93 Effect of BT wt% on the thickness of the spin coated composite film. (Inset shows the structure of the MOS capacitor)……………………………………... 96 (a) Capacitance verses frequency plots for different concentration of BT nanoparticles blended into the SU-8 dielectric films and (b) dependence of resistivity and dielectric constant on BT wt%........................ 96 (a) Schematic cross-section of bottom contact organic field effect transistor with a nanocomposite gate dielectric (b) & (c) transfer (IDS-VGS) &output (IDSVDS) characteristics of pristine SU-8 gate dielectric, and (d) & (e) transfer & output characteristics of composite SU-8 with 0.88 BT wt% gate dielectric (W/L=24000 µm/50 µm)……………………………………………………….. 97 Shows AFM images of (a) pristine SU-8 and (b) 0.88 BT wt% in SU-8/BT nanocomposite………………………………………………………………….. 98 (a) Cross-sectional structure of the organic inverter after semiconductor layer formation (b) Schematic of all p-type organic inverter with enhancement mode driver (M1) and Load (M2), and (c) DC transfer characteristics of a typical organic inverter…………………………………………………………………. 99 5.1 Signal conditioning block diagram……………………………………………... 102 5.2 Schematic cross-section of a bottom-gate-bottom contact p-type OFET with P3HT as its active material [122].…………........................................................ 102 5.3 Response of the OFET with radiation.………………………………………….. 103 5.4 Emulated radiation sensor and its result by simulation………………………… 103 5.5 Transimpedance amplifier (TIA) with sensor block and its response………….. 104 5.6 (a) Cross-section of OTFT device (b) measured vs. LUT simulated output characteristics for OTFTs………………………………………………………. 106 4.3 4.4 4.5 4.6 4.7 x 5.7 5.8 5.9 5.10 (a) P-type OTFT inverter and (b) transient response of the simulated p-type enhancement-mode organic inverter for VDD = 4 V……………………………. 107 (a) Differential inverter circuit using four p-type transistors (b) LUT-based simulation results of the switching characteristic of the inverter for higher values of VIN, the output voltage tends to saturate to the threshold voltage of M2………………………………………………………………………………. 108 Block diagram of the ADC circuit synthesized using the voltage divider and the differential inverter circuit………………………………………………….. 109 (a) Cascade circuit of a differential and simple inverter for each single bit of ADC (b) simulation results of the ADC………………………………………... 109 xi List of Tables 2.1 Parameter comparison for different conducting polymers……....... 15 2.2 Contact angle values after different surface treatments on SiO2 samples……………………………………………………………. 26 2.3 Roughness measurements after different surface treatments……... 28 2.4 Mobility and threshold voltage comparison after different surface treatments…………………………………………………………. 30 Contact angle values and roughness measurements after different surface treatments on HfOx samples………………………………. 31 Mobility, threshold voltage and Ion/Ioff ratio comparison after surface treatment………………………………………………….. 33 Summary of comparative study of transistors based on pristine P3HT and P3HT/ZnO nanocomposites…………………………… 39 2.8 Roughness measurements after porphyrin SAM treatment [35]….. 52 2.9 Various parameters for different device structures……………….. 56 3.1 Measured parameters for the fabricated device with HfOx as gate dielectric…………………………………………………………... 63 3.2 SPICE parameters extracted extracted for P3HT OTFT………….. 66 3.3 Measured parameters forthe fabricated device with SiOx as gate dielectric…………………………………………………………... 67 3.4 Measured parameters for the fabricated device………………….... 69 3.5 Material parameters for pentacene semiconductor [97]…………... 73 3.6 Defects location and density in pentacene films. All defects are Gaussian and acceptor type. Location is w.r.t. valence band [97].. 73 3.7 Device dimensions and measured parameters of the device……… 74 3.8 Spice parameters extracted after matching…………………........... 74 3.9 Device related parameters by experiment………………………… 80 3.10 SPICE parameters extracted after matching………………………. 80 4.1 Summary of dielectric optimization……………………………..... 90 2.5 2.6 2.7 xii Abbreviations and Nomenclature ADC - Analog to Digital Converter AFM - Atomic Force Microscopy Al2O3 - Aluminum oxide Al - Aluminium Au - Gold BDFO - Bi0.7Dy0.3FeO3 BEOL - Back End Of Line BGBC - Bottom Gate Bottom Contact BGTC - Bottom-Gate Top-Contact BT - Barium Titanate CNT - Carbon Nanotubes Cr - Chromium CuPc - Copper phthalocyanine CV - Capacitance-Voltage FTIR - Fourier Transform Infrared Spectroscopy HfOx - Hafnium oxide HMDS - Hexamethyldisilazane. HMTA - Hexamethylenetetramine HOMO - Highest Occupied Molecular Orbital ICPCVD - Inductively Coupled Plasma Chemical Vapor Deposition IGFET - Insulated Gate Field-Effect Transistor IPA - Isopropyl Alcohol ITO - Indium Tin Oxide IV - Current-Voltage LPCVD - Low-Pressure Chemical Vapor Deposition LUMO - Lowest Unoccupied Molecular Orbital LUT - Look-up Table MIS - Metal Insulator Semiconductor MOS - Metal Oxide Semiconductor xiii MOCVD - Metal organic Chemical Vapor Deposition MTR - Multiple Traps and Release NTCDA - 1,4,5,8-naphthalene tetracarboxylicdianhydride NTCDI - 1,4,5,8-naphthalene tetracarboxylicdiimide OFET - Organic Field Effect Transistors OLED - Organic Light Emitting Diodes OPVD - Organic Photovoltaic Diodes OTFT - Organic Thin Film Transistors OTS - Octadecyltrichlorosilane P3HT - poly (3-hexylthiophene) PEB - Post exposure bake PLD - Pulsed Laser Deposition PMMA - Polymethyl Methacrylate PSO - Particle Swarm Optimization PTCDA - Perlenetetracarboxylic Dianhydride PVD - Physical Vapor Deposition RCA - Radio Corporation of America RFID - Radio-frequency identification RT - Room temperature RTA - Rapid Thermal Annealing S - Subthreshold Swing SAED - Selected Area Electron Diffraction SAM - Self-Assembled Monolayer SEM - Scanning Electron Micrographs SiNx - Silicon Nitride SEQUEL - Solver for circuit EQuations with User-defined Elements SiO2 - Silicon dioxide SPICE - Simulation Program with Integrated Circuit Emphasis TCNNQ - 11,11,12,12-tetracyanonaphtho-2,6-quinodimethane TDEAH - Tetrakis Diethylamido Hafnium TEM - Transmission Electron Microscope TGBC - Top-Gate Bottom-Contact xiv Ti - Titanium TIA - Transimpedance Amplifier VLS - Vapor-Liquid-Solid VRH - Variable Range Hopping XRD - X-Ray Diffraction VLSI - Very Large Scale Integration UV-Vis - Ultraviolet-Visible ZnCl3 - Zinc Chloride ZnO - Zinc Oxide μ - Mobility COX - Gate Oxide Capacitance W - Channel Width L - Channel Length IDS - Drain source current VGS - Gate Source Voltage VDS - Drain Source Voltage VT - Threshold Voltage VTO - Turn-on/onset Voltage VIN - Input voltage of inverter VOUT - Output voltage of inverter VDD - Supply Voltage of inverter xv