Supercritical fluid electrodeposition of elemental germanium onto titanium nitride substrates
Supercritical fluid electrodeposition of elemental germanium onto titanium nitride substrates
 
  We report the electrodeposition of germanium from supercritical difluoromethane (sc-CH2F2) at 19 MPa and 358 K using [NnBu4][GeCl3]. Voltammetry shows a classic nucleation loop on the first anodic scan with a high nucleation overpotential for germanium on TiN. In all cases the deposition appears to be kinetically limited by a coupled, potential independent, chemical step. Films of germanium were deposited at a range of potentials. At high overpotentials the films were dendritic and poorly adherent. At lower overpotentials, below ?2 V vs. Ag|LaF3, the films are smoother and more homogeneous. Analysis of the films by energy dispersive X-ray (EDX) spectroscopy shows the presence of germanium with some chloride impurity. Raman spectroscopy confirms the deposition of amorphous germanium. Plating by pulsing to ?1.9 V vs. Ag|LaF3 for 100 ms and then growth at ?1.5 V vs. Ag|LaF3, was found to produce the best films. On annealing at 700°C under an Ar atmosphere for 1 hour the as-deposited amorphous germanium film is converted into crystalline germanium, as determined by X-ray diffraction (XRD) and Raman spectroscopy.
  difluoromethane, electrodeposition, germanium, supercritical fluid, titanium nitride
  
  
  D619-D624
  
    
      Cummings, Charlie
      
        37ed515b-eb09-4c6b-9c66-61013c8c132a
      
     
  
    
      Bartlett, Philip N.
      
        d99446db-a59d-4f89-96eb-f64b5d8bb075
      
     
  
    
      Pugh, David
      
        9ec61267-ae4d-40d8-bebf-0d603e2588d3
      
     
  
    
      Reid, Gillian
      
        37d35b11-40ce-48c5-a68e-f6ce04cd4037
      
     
  
    
      Levason, William
      
        e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
      
     
  
    
      Hasan, Mahboba M.
      
        fdb892ba-7f72-4e59-98c1-f070733840c9
      
     
  
    
      Hector, Andrew L.
      
        f19a8f31-b37f-4474-b32a-b7cf05b9f0e5
      
     
  
    
      Spencer, Joe
      
        a6c29a03-e851-4598-a565-6a92bb581e70
      
     
  
    
      Smith, David C.
      
        d9b2c02d-b7ea-498b-9ea1-208a1681536f
      
     
  
  
   
  
  
    
    
  
    
      16 October 2015
    
    
  
  
    
      Cummings, Charlie
      
        37ed515b-eb09-4c6b-9c66-61013c8c132a
      
     
  
    
      Bartlett, Philip N.
      
        d99446db-a59d-4f89-96eb-f64b5d8bb075
      
     
  
    
      Pugh, David
      
        9ec61267-ae4d-40d8-bebf-0d603e2588d3
      
     
  
    
      Reid, Gillian
      
        37d35b11-40ce-48c5-a68e-f6ce04cd4037
      
     
  
    
      Levason, William
      
        e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
      
     
  
    
      Hasan, Mahboba M.
      
        fdb892ba-7f72-4e59-98c1-f070733840c9
      
     
  
    
      Hector, Andrew L.
      
        f19a8f31-b37f-4474-b32a-b7cf05b9f0e5
      
     
  
    
      Spencer, Joe
      
        a6c29a03-e851-4598-a565-6a92bb581e70
      
     
  
    
      Smith, David C.
      
        d9b2c02d-b7ea-498b-9ea1-208a1681536f
      
     
  
       
    
 
  
    
      
  
  
  
  
  
  
    Cummings, Charlie, Bartlett, Philip N., Pugh, David, Reid, Gillian, Levason, William, Hasan, Mahboba M., Hector, Andrew L., Spencer, Joe and Smith, David C.
  
  
  
  
   
    (2015)
  
  
    
    Supercritical fluid electrodeposition of elemental germanium onto titanium nitride substrates.
  
  
  
  
    Journal of the Electrochemical Society, 162 (14), .
  
   (doi:10.1149/2.0771514jes). 
  
  
   
  
  
  
  
  
   
  
    
    
      
        
          Abstract
          We report the electrodeposition of germanium from supercritical difluoromethane (sc-CH2F2) at 19 MPa and 358 K using [NnBu4][GeCl3]. Voltammetry shows a classic nucleation loop on the first anodic scan with a high nucleation overpotential for germanium on TiN. In all cases the deposition appears to be kinetically limited by a coupled, potential independent, chemical step. Films of germanium were deposited at a range of potentials. At high overpotentials the films were dendritic and poorly adherent. At lower overpotentials, below ?2 V vs. Ag|LaF3, the films are smoother and more homogeneous. Analysis of the films by energy dispersive X-ray (EDX) spectroscopy shows the presence of germanium with some chloride impurity. Raman spectroscopy confirms the deposition of amorphous germanium. Plating by pulsing to ?1.9 V vs. Ag|LaF3 for 100 ms and then growth at ?1.5 V vs. Ag|LaF3, was found to produce the best films. On annealing at 700°C under an Ar atmosphere for 1 hour the as-deposited amorphous germanium film is converted into crystalline germanium, as determined by X-ray diffraction (XRD) and Raman spectroscopy.
         
      
      
        
          
            
  
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      Accepted/In Press date: 29 September 2015
 
    
      Published date: 16 October 2015
 
    
  
  
    
  
    
  
    
  
    
  
    
  
    
     
        Keywords:
        difluoromethane, electrodeposition, germanium, supercritical fluid, titanium nitride
      
    
  
    
     
        Organisations:
        Chemistry
      
    
  
    
  
  
        Identifiers
        Local EPrints ID: 385448
        URI: http://eprints.soton.ac.uk/id/eprint/385448
        
          
        
        
        
          ISSN: 0013-4651
        
        
          PURE UUID: 67d87ede-d5ff-4caf-957d-36a561bab2a4
        
  
    
        
          
        
    
        
          
            
              
            
          
        
    
        
          
        
    
        
          
            
              
            
          
        
    
        
          
            
              
            
          
        
    
        
          
            
          
        
    
        
          
            
              
            
          
        
    
        
          
            
          
        
    
        
          
            
          
        
    
  
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  Date deposited: 20 Jan 2016 09:03
  Last modified: 22 Aug 2025 01:41
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      Contributors
      
          
          Author:
          
            
            
              Charlie Cummings
            
          
        
      
        
      
          
          Author:
          
            
            
              David Pugh
            
          
        
      
        
      
        
      
          
          Author:
          
            
              
              
                Mahboba M. Hasan
              
              
            
            
          
        
      
        
      
          
          Author:
          
            
              
              
                Joe Spencer
              
              
            
            
          
        
      
        
      
      
      
    
  
   
  
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