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Water Soluble Nano-Scale Transient Material Germanium Oxide for Zero Toxic Waste Based Environmentally Benign Nano-Manufacturing

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Water Soluble Nano-Scale Transient Material Germanium Oxide for Zero Toxic Waste Based Environmentally Benign Nano-Manufacturing Water soluble nano-scale transient material germanium oxide for zero toxic waste based environmentally benign nano-manufacturing Item Type Article Authors Almuslem, A. S.; Hanna, Amir; Yapici, Tahir; Wehbe, N.; Diallo, Elhadj; Kutbee, Arwa T.; Bahabry, Rabab R.; Hussain, Muhammad Mustafa Citation Almuslem AS, Hanna AN, Yapici T, Wehbe N, Diallo EM, et al. (2017) Water soluble nano-scale transient material germanium oxide for zero toxic waste based environmentally benign nano- manufacturing. Applied Physics Letters 110: 074103. Available: http://dx.doi.org/10.1063/1.4976311. Eprint version Publisher's Version/PDF DOI 10.1063/1.4976311 Publisher AIP Publishing Journal Applied Physics Letters Rights Archived with thanks to Applied Physics Letters Download date 24/09/2021 18:56:53 Link to Item http://hdl.handle.net/10754/622963 Water soluble nano-scale transient material germanium oxide for zero toxic waste based environmentally benign nano-manufacturing A. S. Almuslem, A. N. Hanna, T. Yapici, N. Wehbe, E. M. Diallo, A. T. Kutbee, R. R. Bahabry, and M. M. Hussain Citation: Appl. Phys. Lett. 110, 074103 (2017); doi: 10.1063/1.4976311 View online: http://dx.doi.org/10.1063/1.4976311 View Table of Contents: http://aip.scitation.org/toc/apl/110/7 Published by the American Institute of Physics Articles you may be interested in Zinc tin oxide metal semiconductor field effect transistors and their improvement under negative bias (illumination) temperature stress Appl. Phys. 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Hussain1,a) 1Integrated Nanotechnology Lab and Integrated Disruptive Electronic Applications (IDEA) Lab, Electrical Engineering, Computer Electrical Mathematical Science and Engineering Division, King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Saudi Arabia 2Analytical Chemistry Lab and Imaging and Characterization Lab, KAUST Core Facilities, KAUST, Thuwal, Saudi Arabia 3Integrated Nanotechnology Lab and Integrated Disruptive Electronic Applications (IDEA) Lab, Material Science and Engineering, Physical Science and Engineering Division, King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Saudi Arabia (Received 4 December 2016; accepted 25 January 2017; published online 14 February 2017) In the recent past, with the advent of transient electronics for mostly implantable and secured electronic applications, the whole field effect transistor structure has been dissolved in a variety of chemicals. Here, we show simple water soluble nano-scale (sub-10 nm) germanium oxide (GeO2) as the dissolvable component to remove the functional structures of metal oxide semiconductor devices and then reuse the expensive germanium substrate again for functional device fabrication. This way, in addition to transiency, we also show an environmentally friendly manufacturing pro- cess for a complementary metal oxide semiconductor (CMOS) technology. Every year, trillions of complementary metal oxide semiconductor (CMOS) electronics are manufactured and billions are disposed, which extend the harmful impact to our environment. Therefore, this is a key study to show a pragmatic approach for water soluble high performance electronics for environmentally friendly manufacturing and bioresorbable electronic applications. Published by AIP Publishing. [http://dx.doi.org/10.1063/1.4976311] Transient electronics have received growing attention properties such as high carrier mobility (up to 3900 cm2 VÀ1 recently owing to its dissolvability for implantable and sÀ1 for electrons and 1900 cm2 VÀ1 sÀ1 for holes),6 direct secured electronic applications.1,2 In these examples, the and small energy band gap (0.66 eV), small optical band gap whole structure is dissolved over the time in a variety of (wide absorption wavelength spectrum), and low dopant chemicals. Here, we show that water soluble germanium thermal activation energies in comparison with the universal 7 dioxide (GeO2) can be employed as a transient material CMOS material Silicon (Si). As a result of unique proper- besides its function as a dielectric layer. The usage of GeO2 ties, Ge becomes the material of choice for manufacturing as the dissolvable material will still remove the key structure high speed, low power devices,8 as well as optoelectronic to serve the purpose of dissolution. At the same time, since it devices.9 is simply water soluble, we can reuse the expensive germa- In this work, water soluble GeO2 is a hallmark since it nium (Ge) substrate for further device fabrication. serves two different purposes as it allows for both recycling GeO2 can have three forms, two of them are crystalline the substrate and reducing the pollution originated from dis- and the third one is vitreous. Crystalline forms are repre- carded consumer electronics. We show that it would be of 3 sented by hexagonal and tetragonal crystalline structures. great benefit to meet the rapid growth demands for consumer The growth conditions determine the resultant form of GeO2, electronics and keeping the electronic waste at bay simulta- 4 and the difference between them was reported by Johnson. neously. Electronic waste is reported to be up to 42 Â 106 10 Only hexagonal and vitreous form is water soluble. The tons yearly. Moreover, water as an etchant of GeO2 is hydrolysis mechanism of GeO2 undergoes the following highly preferable to other wet reactive chemicals as water is 5 chemical reaction: used frequently in the IC fabrication process for cleaning and etching purposes because: (i) it does not have an envi- GeO þ H O $ H GeO : (1) 2 ðsÞ 2 ðlÞ 2 3ðaq:Þ ronmental impact, (ii) it is safe to handle easily, and (iii) it is 11 Surface oxidation of Ge has been considered as an unde- relatively of low-cost. On the other hand, the Ge/GeO2 sirable feature, which prevents Ge to be incorporated in the interface has a variety of satisfactory properties such as acceptable dielectric constant (j ¼ 2.8),12 moderate refrac- Complementary Metal Oxide Semiconductor (CMOS) indus- 13 try for a long time. However, many studies have addressed a tive index, and adequate thermal stability. Besides that, surface passivation challenge for the purpose of making use GeO2 has the advantage of suppressing the Ge dangling of superior material properties of Ge. Ge possesses favorable bond at the surface, which in turn minimizes the interface trap density.14 a)Author to whom correspondence should be addressed. Electronic mail: In this study, Metal Oxide Semiconductor Capacitors [email protected] (MOSCAPs) are built on p-type Ge substrates using GeO2 as 0003-6951/2017/110(7)/074103/5/$30.00 110, 074103-1 Published by AIP Publishing. 074103-2 Almuslem et al. Appl. Phys. Lett. 110, 074103 (2017) a dielectric layer. After characterizing the capacitors, the sub- (GeO2 grown after the first GeO2 has been removed). XPS strate is rinsed with tap water in order to dissolve GeO2,which peaks of GeO2 grown and GeO2 regrown samples are identi- in turn takes away all the top layers. The substrate is then cal and reveal a clear shift with respect to the reference sam- effectively reused to build the similar MOSCAPs again. GeO2 ple. Indeed, the 2p3/2 and 3d5/2 photoemission lines are is thermally grown on a p-type Ge (Ga-doped) 175 lmthick shifted by 2.8 eV and 3.5 eV, respectively, toward higher substrate with resistivity ranging from 0.01 to 0.05 X cm. binding energy, which is specified to the fourth oxidation þ4 We start with 4-in. Ge wafer, which is then diced up to state (Ge ) of Ge and confirms the existence of the GeO2 2 Â 2cm2 experimental samples. Then, the pieces are cleaned layer.7,13,16,17 However, the spectrum acquired for the refer- with HF (49%), rinsed with Deionized (DI) water, blown ence germanium substrate is very similar to the one belong- driedinNitrogen(N2), followed by acetone and isopropanol ing to the rinsed sample, suggesting that both layers have the based cleaning, and blown dried in N2. After that, the proc- same composition. The quantitative data indicate that the ref- essed experimental samples are transferred into an Ultra High erence and rinsed samples are composed of almost 50% of Vacuum Chemical Vapor Deposition (UHVCVD) chamber in germanium and 50% of oxygen, whereas the grown and order to grow GeO2. The chamber’s temperature is stabilized regrown layers contain 67% of oxygen and 33% of germa- at 400 Cfor4hinOxygen(O2) ambient with a flow rate of nium. Precisely speaking, the major components of Ge 2p3/2 100 sccm. and Ge 3d5/2 of the reference and rinsed samples are X-ray Photoemission Spectroscopy (XPS) was used to detected, respectively, at 1218 eV and 29.6 eV. These values verify the substrate surface properties for a clean Ge surface, can be assigned to metallic germanium Ge.7,13,16,17 The grown GeO2 layer, GeO2 removal, and regrown GeO2 layer smaller component detected mainly for Ge 2p3/2 at 1219.8 as it is capable to provide the chemical composition.15 XPS can be assigned to germanium monoxide (GeO). Hence, the experiments were performed on a KRATOS Analytical most probable chemical composition of both reference and AMICUS instrument equipped with an achromatic Al Ka rinsed layers can be described by a thin over layer of native X-ray source (1468.6 eV).
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