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Special Report                                                                   Special Report


 inerting  and purging gas, protecting  Oxygen  local electrical properties of the semi-  Table 1: Major semiconductor gases  qualifi ed  remote  sources,  as  well  as
 sensitive silicon wafers from reactive   Oxygen is used for the oxidation of  conductor material.  The list includes   Atmospheric  Silicon precursor   Etchant gases  Dopant gases  liquid storage on-site equivalent  to
 oxygen and moisture in the air.  silicon, one of the most critical processes  arsine,  boron  trifl uoride,  diborane,   gases  gases  several days of production demand.
 in all of semiconductor manufacturing.  phosphine and trimethylboron.
 To meet this demand, semiconductor   Nitrogen  Dichlorosilane  Boron trichloride  Arsine  Market trends
 manufacturing plants often install  Silicon precursor gases  Specifi cally,  a  dopant  contributes   Oxygen  Disilane  Chlorine  Boron trifl uoride  Growth  in consumption of specia-
 nitrogen generators onsite to ensure   Silicon-precursor gases  act as  a  either an electron defi ciency (p-dopant)   Hydrogen  Germane  Halocarbons 116,   Diborane  lity gases (and other fab chemicals)
 a  cheap,  effi cient,  and  always-ready  source of silicon atoms for the deposi-  or an electron (n-dopant) to the local   14, 218, 23, 32,   is directly driven by the construction
 supply of nitrogen gas.  tion of polycrystalline silicon, epitaxial  structure of the molecule’s crystal lat-  RC318   of several new semiconductor fabs all
 silicon, silicon dioxide, and silicon  tice, which, in turn, alters the conduc-  Argon  Germanium tetrafl uoride Hydrogen bromide  Phosphine  over the world. Because modern chip
 Helium  nitride.  The most common gases are  tivity of the material. Dopants are avai-  Helium  Methylsilane  Hydrogen chloride  Trimethylboron  fabs require huge investments, they are
 Helium is particularly  useful in  silane,  dichlorosilane,  trichlorosilane,  lable in liquid, solid and gaseous states.   often supported by government  poli-
 semiconductor  manufacturing,  to  and silicon tetrachloride.  Dopants are used in epitaxial  deposi-  Silane  Hydrogen fl uoride  cies such as the US CHIPS and Science
 effi ciently  conduct  heat  away  from   tion, diffusion and ion implantation.  Silicon tetrachloride  Nitrogen trifl uoride  Act, the European Chips Act, and other
 energetic processes  and help pro-  Silane and dichlorosilane are used in   Silicon tetrafl uoride  Sulphur hexafl uoride  incentive  schemes such as those an-
 tect them from thermal  damage and  epitaxial and chemical vapour deposi-  A common gaseous p-dopant is   Trichlorosilane  nounced in India. Governmental sup-
 unwanted chemical reactions.  tion (CVD) processes to deposit layers  diborane, while arsine is used for   port has gained importance  since the
 of  silicon or  silicon  compounds onto  n-type doping.  major factors that drive the supply of  transportation is  therefore the  overall  major global semiconductors supply
 Hydrogen  silicon substrates. Silicon epitaxial lay-  bulk gases.  cost  driver;  products  are  liquefi ed  for  shortage seen in 2021 and 2022.
 In semiconductor production hydro-  ers are formed in reactions based on the   A major growth area for arsine and   transportation and  then  vaporized on-
 gen is used for:  mechanisms of thermal decomposition  phosphine use is the  fabrication of   Air separation is the primary set of  demand for use.  According to Linx Consulting, the
    Annealing: Silicon wafers are rou-  or reduction by hydrogen, depending on  wafers called  ‘III-V devices,’ using a   processes used to obtain nitrogen, oxy-  semiconductor industry consumed $3-bn
 tinely heated to  high  temperatures  the silicon-precursor reactant gas used.  vapour phase epitaxy (VPE) or, more   gen, and argon from air. Moisture, car-  Scale is the determiner  for on-site  worth of electronic specialty  gases in
 and slowly cooled in order to   frequently, the metal organic chemical   bon dioxide, and other impurities are  production  vs. truck  delivery. For  2020 compared to $2.5-bn in 2019.
 repair (anneal) the crystal structure.   Each silicon-precursor gas has epi-  vapour deposition (MOCVD) method.  fi rstly removed from the air by chemi-  nitrogen, almost all 300-mm fabs and
 Hydrogen is used to transfer heat  taxial processing  advantages and  dis-  cal absorbers. The air is then cooled by  new display fabs operate at scales that   Major suppliers include global com-
 uniformly to the wafer and assist  advantages, including processing tem-  Etchant gases  successively compressing and expand-  require on-site production of nitrogen:  panies such as  Air Liquide,  Air Pro-
 the reconstruction of the crystal  perature range, degree of  auto-doping   Etchant gases include fl uorocarbons   ing it until it turns into a liquid, which  to reduce cost; to ensure robust supply;  ducts, Iwatani, Linde, SK Materials and
 structure.  and growth rates.  and  other  fl uorinated  materials.  The   is then distilled into these three com-  and to produce to the highest and most  Versum. There is, however, an oppor-
    Epitaxy: Ultra-high purity hydro-     Silane is used throughout a fab in  most important  gases today are halo-  ponents. Electronics-grade air separa-  consistent purity standards. Often, the  tunity in the market for smaller, more
 gen is used as a reducing agent in   numerous CVD processes to form  carbon  14  (tetrafl uoromethane),  halo-  tion units can produce these gases to  demand  for ultra-high purity oxygen  focused providers of high-purity appli-
 the epitaxial deposition of semicon-  oxide, nitride and polysilicon thin fi lms.  carbon 23 (trifl uoromethane), halocarbon   >99.999999% purity. Because argon  requires an  on-site plant to  achieve  cations and differentiated compression
 ductor materials such as silicon and   Dichlorosilane,  in a gaseous state  116  (hexafl uoroethane),  and  nitrogen   makes up only 1% of air by volume,  the required purity specifi cations. And  capabilities.  Diffi cult-to-source  and

 germanium.  at 0.5 atmosphere, is also a primary  trifl uoride.  These  etchant  gases  react   it is often not economically sensible to  at leading-edge semiconductor  plants,  diffi cult-to-handle  materials  can  also
    Deposition: Hydrogen can be   source for polysilicon deposition.  with silicon, silicon dioxide and silicon   produce with smaller plants.  the use of epitaxial processes and the  provide a major point of differentiation
 incorporated into thin silicon fi lms   Trichlorosilane and  silicon tetra-  nitride.  adoption of EUV lithography are twin  for specialty gas providers.

 to make their atomic structure more   chloride are both corrosive liquids   It takes about three times as much  drivers affecting consideration of
 disordered and help increase  their   at room temperature and pressure.  Halocarbons are used typically to   electricity to produce these products as  on-site hydrogen production.  In March 2023, the Semiconductor
 electrical resistivity.     Methylsilane is used for deposition  etch silicon compounds, whereas the   liquids compared to the gas phase. For   Solutions business Merck KGaA, started
    Plasma cleaning: Hydrogen plasma   of silicon carbide fi lms.  other chlorine and fl uorine compounds   gases made on-site, it is therefore most   In certain locations, fabs are co-  construction of a new manufacturing
 is particularly effective at removing   Germane is used for silicon-germanium  are usually required for etching metal-  economical to produce most as gases,  located  into clusters.  This allows  for  site in Kaohsiung, Taiwan. This project

 tin contamination from light sources   epitaxy for bandgap modifi cation.  lic interconnects.  which are supplied on-demand imme-  even greater economies of scale, as a  will manufacture speciality  gases and
 used in UV photolithography.  diately to the fab, with a small portion  pipeline can network  the supply from  semiconductor  materials  for  thin  fi lm
 There is increasing use of dichloro-  The choice of gas strongly depends   liquefi ed  for  storage  and  redundant  larger gas plants to multiple customers.  and patterning starting 2025.
 Argon  silane over the  high-deposition tem-  on the ability of a given mixture of   supply.
 Because argon is comparatively  perature trichlorosilane and  silicon  gases to selectively etch one fi lm in the   Regardless of  the primary supply,   In  April 2023, EMD Electronics,
 easy to ionise, it is commonly used as  tetrachloride.  presence  of  another  with  a  suffi cient   However,  because  gases are  much  electronics  production  requires  the electronics subsidiary  of  Merck,
 a primary plasma gas for etching and   degree of profi le control.  less  dense  than  liquids,  it  takes  fi ve  extremely high guarantees of  supply;  announced it will spend $300-mn to
 deposition reactions in semiconductor  Dopant gases  trucks to deliver the same amount  therefore, redundant sources and sup-  expand  its specialty  gas production
 fabrication.  In addition, argon is used   Dopant gases are a source of con-  Supply chains  of gas-phase  product  as one truck  ply schemes are put in place. Most  facility in eastern Pennsylvania (USA).
 in excimer lasers for UV lithography.  trollable impurities used to modify the   Scale, purity, reliability and cost are   of liquid-phase product.  The  cost of  often, this means having one or more  The expansion will create the world’s


 176  Chemical Weekly  February 20, 2024  Chemical Weekly  February 20, 2024                           177


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