Chapter Fabrication and experimental setups This chapter outlines the experimental techniques used in subsequent chapters. Section 3.1 describes two different graphene film synthesis approaches which are used in this dissertation; section 3.2 presents the process of fabricating GFET devices, which will be the starting point for experiments covered from chapter to chapter 7; Section 3.3 presents the preparation of ferroelectric thin films, which will be used in experiments from chapter to chapter 6; Section 3.4 is devoted to charge transport measurement schemes used throughout the rest of the thesis. 3.1 Graphene fabrication Since its first discovery, the synthesis and growth of graphene films has been central to graphene research and its potential applications. Here we introduce two different approaches to graphene synthesis. 25 26 Bilayer Multi-layer Single layer SiO2 substrate Figure 3.1: Optical image of single layer, bilayer and multilayer graphene on Si/SiO2 substrate. The scale-bar is 10 μm. 3.1.1 Mechanical exfoliated graphene Graphene is obtained by the mechanical exfoliation method from Kish graphite sources. Adhesive tape (Scotch tape) is used as a holder of the graphite source and repeti- tive folding and peeling processes are required in order to split graphite crystals into increasingly thinner pieces. When these graphite pieces are thin enough (optically transparent), they are directly transferred onto Si/SiO2 substrate by rubbing at the back side of these graphite piece through the tape. Finally, the supporting tape is gently peeled off from the Si/SiO2 substrate, leaving tiny pieces of graphene as well as small graphite randomly distributed on the top of the SiO2 surface. After cleaving, optical microscopy is used for preliminary identification of graphene as shown in Fig. 3.1. Based on the contrast difference, one can distinguish single layer and few layer graphene on SiO2 substrates. Raman spectroscopy or atomic force 27 microscopy is used to further verify the exact graphene layer number and quality. Wavelength (nm) a 0.15 0.00 Thickness (nm) b Contrast 0.15 0.10 0.05 0.00 100 200 300 400 Wavelength (nm) Figure 3.2: (a) Color plot of the contrast as a function of wavelength and SiO2 thickness (reproduced using equals in [79]). (b) Extracted single contrast curve as a function of SiO2 thickness, the corresponding wavelength is 550 nm. The reason why one can see monolayer graphene with the naked eye is due to the interference effect induced by the SiO2 layer. Indeed, the thickness of the SiO2 layer significantly affects the visibility of monolayer graphene, as shown in Fig. 3.2. As we can see clearly, 285 nm and 90 nm thickness SiO2 layer provide the best contrast 28 for the detection of graphene flakes with bare eyes. Using this model, one can also identify the visibility of graphene on other substrates [79]. 3.1.2 Chemical vapor deposition of graphene Temperature ( C) a O Time (min) b c Figure 3.3: (a) Growth parameters of large-scale graphene using chemical vapor deposition method; (b) Optical image of thermal furnace and copper foils for graphene growing. (c) 30-inch large-scale graphene after transferred onto transparent substrates [44, 50]. Although the mechanical exfoliation method can provide single crystal graphene flakes, this method is not a scalable technique. The mechanically exfoliated graphene films is limited to small sizes (usually ≈ 1000 μm2 ), thus incompatible with industrial requirements. To address this challenge, significant efforts have been devoted to 29 Figure 3.4: Optical image of a graphene field effect transistor devices on Si/SiO2 substrates. develop graphene synthesis at a large scale. Among the different approaches, chemical vapor deposition method exhibits very promising results. Using this method, thirty inch graphene membranes with decent electronic quality have been demonstrated recently, as shown in Fig. 3.3 [44]. The working principle of this method essentially follows the bottom up strategy. The growth of graphene begins from the assemblage of carbon atoms at elevated temperature under certain gas flows. Using a copper substrate, graphene is grown by a surface-catalyzed process rather than a precipitation process, making large-scale monolayer graphene continuous and uniform [44]. To grow wafer scale uniform monolayer graphene, a carbon-containing stock gas, i.e., benzene, ethane or methane is injected into the high temperature furnace and undergoes a dehydrogenation process on a catalytic surface such as Cu or Ni. As a result, the carbon atoms rearrange into a honeycomb lattice [49, 50, 80]. 30 3.2 Fabrication of graphene field effect transistor GFET 3.2.1 GFET devices using mechanically exfoliated graphene After graphene is transferred onto a 300 nm SiO2 over doped silicon, it is ready to be fabricated into devices for electrical transport studies. The position of graphene flakes is determined with respect to pre-defined alignment marks. A single layer of 495 K molecular weight Polymethyl Methacrylate (PMMA) is spin-coated at 4000 rpm onto the samples, then baked at 180 o C for minutes. A subsequent standard electron beam lithography (EBL, 30 KeV) process locates the graphene samples and defines thermally evaporated electrodes (Cr/Au = 5/30 nm) on top, followed by a liftoff process in acetone. Depending on the needs of specific experiments, the contact pads are designed to either Hall-bar geometry or four-terminal configuration (Fig. 3.4). Sometimes, a second EBL step is performed to pattern graphene into a specific shape followed by oxygen plasma etching. The doped silicon is used as the gate electrode (back gate) and the SiO2 as the gate dielectric in transport measurements. Although the back gate provided by heavily doped silicon yields many interesting transport phenomena [17, 81], it represents only the first step towards more complex graphene devices. Thus, fabrication of dual gated structures such as lateral graphene p-n or p-n-p junction devices is sorely needed for further studies [19, 39, 82]. Figure 3.5 shows the ferroelectric top gated device structure using the metal mask approach. The top dielectric that we are using is ferroelectric copolymer P(VDF-TrFE). 31 a b Figure 3.5: (a) Schematics of a graphene-ferroelectric p-n-p junctions; (b) Optical image of a graphene-ferroelectric p-n-p junction device fabricated using metal mask method. Scale bar is μm. 3.2.2 GFET devices made out of chemical vapor deposition graphene Unlike the mechanically exfoliated graphene, the chemical vapor deposition method makes monolayer graphene much more easily accessible. After CVD graphene growth, a thin layer of PMMA resist is coated on top of the graphene/copper structure, after which the copper foil is etched using Ammonium Persulfate (APS). With the mechanical support from PMMA, the PMMA/graphene hybrid structure can be easily transferred to any other substrate [50]. After standard EBL process and thermal evaporation, a second EBL step is required to pattern the etching channel, followed by oxygen plasma treatment to isolate the electrodes. Taking advantage of the largescale nature of CVD graphene, dozens of graphene devices can be fabricated within a single chip, thus enhancing the device yield, as shown in Fig. 3.6. 32 etching channel a b Figure 3.6: (a) Optical image of an array of GFET devices on SiO2 substrate. Scale Bar is 500 μm; (b) Hall-bar and four-terminal GFET devices and the patterned etching channel for device separation. Scale Bar is 10 μm. 3.3 Ferroelectric dielectric preparation and characterization In this section we present the preparation and characterization of ferroelectric thin films (ferroelectric organic polymer and inorganic ferroelectrics) used. The ferroelectric organic polymer needed is a copolymer made from poly(vinylidene fluoride) (PVDF) and Trifluorethylene (TrFE) (Available from PIEZOTECH). The P(VDFTrFE) (72/28) precursor solution is made by dissolving polymers in a solvent of mixed dimethylformamide and acetone (1:1 by volume) [83]. The preparation of P(VDF-TrFE) solution consists of the following steps: • Prepare the solvent consisting of a mixture of acetone and DMF with a composition of 50:50 by volume • Add P(VDF-TrFE) to the solvent such that the P(VDF-TrFE) to the solvent has a ratio 10:90 by mass. The specific ratio may be varied for variation in thickness of P(VDF-TrFE) thin film. In our experiments, we utilized 5:95 ratio 33 a Topography y 180 nm 0.0 nm b Topography 70 nm Phase 0.0 nm c Topography 100 nm Phase 0.0 nm d β-phase Figure 3.7: (a) Optical image and AFM scanning of spin-coated P(VDF-TrFE) on graphene flakes. Scale bar is 15 μm. (b), (c) Comparison of P(VDF-TrFE) morphology and phase diagram at short/long annealing time. Scale bars are 400 nm. (d) Comparison of XRD results of both sufficient and insufficient annealed P(VDF-TrFE) film. 34 (500 nm) and 10:90 ratio (1 μm). • Completely dissolve the P(VDF-TrFE) solution at 50 o C for hours. • Apply P(VDF-TrFE) solution onto the substrate and start the spin-coating process. • Dry the spin-coated sample on a hotplate at 100 o C for 10 mins. • Further anneal the sample in an oven at 135 o C for 20 hours. Note that sufficient thermal annealing is critical for the formation of ferroelectric β-phase, as shown in Fig. 3.7a-c. When the annealing time is insufficient, the formation of the ferroelectric phase is poor, limiting its ferroelectric performance. After sufficient annealing, a predominant phase transition from the paraelectric phase to ferroelectric phase transition occurs, leading to the highly crystalline nature of P(VDF-TrFE) film (Fig. 3.7d). Furthermore, the compatibility of P(VDF-TrFE) and ferroelectric inorganic film PZT with commonly used solvent, i.e., MIBK, IPA and Acetone is tested. The results show that P(VDF-TrFE) is compatible with MIBK and IPA. However, either e-beam irradiation or an Acetone rinse will effectively change or remove P(VDF-TrFE) film. As expected, PZT is compatible with MIBK, IPA, Acetone, and e-beam irradiation. 35 3.4 Transport measurements and experimental setups For transport measurements, we used a quasi-DC (low-frequency AC) measurement scheme with four-probe configurations in order to exclude contact resistance. The diagram for the quasi-DC measurement setup is shown in Fig. 3.8a. A lock-in amplifier is used to act as a low frequency signal source. The voltage signal generated by the lock-in amplifier is converted into a current signal determined by V/Rs, given that Rs Rdevice , which is usually the case in measuring graphene. A Keithley source meter is used to provide a gate voltage to tune the carrier density of graphene. The typical values of the resistors used are 10 MΩ and a typical AC frequency used is 13.373 Hz. The measurement configuration technique for the ferroelectric top gated devices is illustrated in Fig. 3.8b. The poling of ferroelectric thin film is realized by the application of a DC voltage to the top contact. In this architecture, graphene serves as the bottom contact for the polarization of ferroelectric thin film. The resistance change of graphene as a function of the ferroelectric polarization is recorded by the lock-in amplifier. The experimental setup for electronic transport measurements in variable temperature insert is shown in Fig. 3.9. Leads from the GFET device are bonded onto the chip carrier using a wire bonder. The chip carrier is then inserted to the sample holder mounted on the VTI probe. The VTI insert is designed such that the sample can be heated up to 400 K for high vacuum thermal annealing, which is critical to removing resist residues and water contaminants. 36 a Computer Digital Singal Lock-in Amplifier b Input A Rs Input B I Rg Keithley Source Meter 6430 Figure 3.8: (a) Schematics of a quasi-DC measurement of the electronic properties of GFET devices. (b) Diagram of a GFeFET device measurement strategies. 37 a b Figure 3.9: Variable temperature insert (VTI) electrical transport measurement setup. (a) Overview of 16T VTI setup; (b) Optical image of the sample holder in the end of the rotating probe. [...]... in measuring graphene A Keithley source meter is used to provide a gate voltage to tune the carrier density of graphene The typical values of the resistors used are 10 MΩ and a typical AC frequency used is 13. 3 73 Hz The measurement configuration technique for the ferroelectric top gated devices is illustrated in Fig 3. 8b The poling of ferroelectric thin film is realized by the application of a DC voltage... contaminants 36 a Computer Digital Singal Lock-in Amplifier b Input A Rs Input B I Rg Keithley Source Meter 6 430 Figure 3. 8: (a) Schematics of a quasi-DC measurement of the electronic properties of GFET devices (b) Diagram of a GFeFET device measurement strategies 37 a b Figure 3. 9: Variable temperature insert (VTI) electrical transport measurement setup (a) Overview of 16T VTI setup; (b) Optical image of the... voltage to the top contact In this architecture, graphene serves as the bottom contact for the polarization of ferroelectric thin film The resistance change of graphene as a function of the ferroelectric polarization is recorded by the lock-in amplifier The experimental setup for electronic transport measurements in variable temperature insert is shown in Fig 3. 9 Leads from the GFET device are bonded onto.. .35 3. 4 Transport measurements and experimental setups For transport measurements, we used a quasi-DC (low-frequency AC) measurement scheme with four-probe configurations in order to exclude contact resistance The diagram for the quasi-DC measurement setup is shown in Fig 3. 8a A lock-in amplifier is used to act as a low frequency signal... device measurement strategies 37 a b Figure 3. 9: Variable temperature insert (VTI) electrical transport measurement setup (a) Overview of 16T VTI setup; (b) Optical image of the sample holder in the end of the rotating probe . section 3. 2 presents the process of fabricating GFET devices, which will be the starting point for experiments covered from chapter 3 to chapter 7; Section 3. 3 presents the preparation of ferroelectric. that we are using is ferroelectric copolymer P(VDF-TrFE). 31 a b Figure 3. 5: (a) Schematics of a graphene -ferroelectric p-n-p junctions; (b) Optical image of a graphene -ferroelectric p-n-p junction. lattice [49, 50, 80]. 30 3. 2 Fabrication of graphene field effect transistor GFET 3. 2.1 GFET devices using mechanically exfoliated graphene After graphene is transferred onto a 30 0 nm SiO 2 over doped