US3742227A - Process and apparatus for the mass spectrometric analysis of surfaces of solids - Google Patents

Process and apparatus for the mass spectrometric analysis of surfaces of solids Download PDF

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Publication number
US3742227A
US3742227A US00088747A US3742227DA US3742227A US 3742227 A US3742227 A US 3742227A US 00088747 A US00088747 A US 00088747A US 3742227D A US3742227D A US 3742227DA US 3742227 A US3742227 A US 3742227A
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ions
solid
primary
ion beam
analyzing
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US00088747A
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English (en)
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A Benninghoven
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Bayer AG
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Bayer AG
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/02—Details
    • H01J49/10—Ion sources; Ion guns
    • H01J49/14—Ion sources; Ion guns using particle bombardment, e.g. ionisation chambers
    • H01J49/142—Ion sources; Ion guns using particle bombardment, e.g. ionisation chambers using a solid target which is not previously vapourised

Definitions

  • ABSTRACT 3 F A Ii P 01 oreign pp canon nomy Data Surfaces of solids, in particular the uppermost mono- NOV. I4, Germany P layer, a e analyzed means of seconda y ion Spec V trometry.
  • the primary ion currents used for bombardfi gii ing the surface of the solid are transmitted at such low E 9 SEn49 g P current densities that the time required for disintegra- I 0 can l tion of a monolayer, in particular the uppermost monolayer of the solid, is long compared with the time taken [56] References Cned for recording a spectrum.
  • the invention relates to aprocess for the mass spectrometric analysis of surfaces of solids by means of secondary ion spectrometry.
  • the process according to the invention is especially suitable for the analysis of the uppermost monolayer of a solid.
  • the surface of the solid is generallyformed by the uppermost monolayer of the solid itself and an adsorption layer lying above it, which is in most cases monomolecular.
  • the distinction between these two layers will now be explained.
  • the uppermost monolayer of the solid may have the same composition as the interior of the solid but it may also contain chemically bound foreign substances or even consist entirely of such substances.
  • the adsorption layer which is not'chemically bound and which is usually'monomolecular, is generally in a state of equilibrium with the surrounding gaseous phase, in other words with the residual gas in the target chamber.
  • the composition of the originally uppermost monolayer of the solid is generally completely different from the interior of the solid, especially in the case of a catalyst.
  • N denotes the number of particles in the closed monolayer
  • j denotes the primary ion current density on the surface of the solid
  • e denotes the elementary charge
  • y denotes the sputtering rate, i.e. the average number of particles of the monolayer removed per incident primary ion.
  • this problem is solved by using such low primary ion current densities for bombardingthe surface of the solid that the time required for sputtering a monolayer of the solid is long compared with the time-for recording a spectrum.
  • the sputtering time of the uppermost monolayer must be long compared with the time taken for recording a spectrum.
  • the process according to the invention is eminently suitable for this purpose if the variation of intensity of the individual types of ions with time is measured during bombardment of the surface of the solid with a constant primary ion density.”
  • FIG. 1 shows an apparatus for carrying out the process according to the invention
  • FIG. 3 shows the secondary ion intensities of individual types of ions during degradation of the upper monolayers of the silver catalyst
  • the method of carrying out the analysis of the uppermost and next following monolayers of a solid will now be described with the aid of the following example of a silver catalyst.
  • the entire vacuum apparatus inclusive the target chamber was made of stainless steel.
  • the flange connections 2.47 between the various elements of the apparatus were sealed with gold wire so that the apparatus could be heated to 450C.
  • the vacuum was generated and maintained by means of two mercury diffusion pumps 8 connected in series. Between the target chamber and the first diffusion pump a cooling trap 9 was inserted which was cooled with liquid nitrogen.
  • a turbo-molecular pump was used instead of the mercury diffusion pumps which has a much higher pumping speed in the ultra high vacuum range especially for noble gas.
  • the analysis was carried out at a total pressure below 10' mm Hg.
  • the main components of the residual gas were H H O, CO and CO Hydrocarbons were practically undetectable.
  • the surface of the catalyst was bombarded with a beam of Ar ions 1 10 amp at an angle of from the perpendicular to the target.
  • the intensity of primary ion current density can best be in the range of about 10'" 10 amp cm", preferably about I0 to 10 amp cm".
  • the degradation times can best be in the range of about 500 h sec, preferably about 50 h 5 h.
  • the ratio of degradation time and the spectrum reading time can best be in the range of about 5,000 0,5, preferably 500 50.
  • the Ar ions are generated by a plasma-type ion source similar to that described by Finkelstein in Rev. Sci. Instr. Il,95(l940).
  • quadrupole mass filter instead of the 60-sector field mass spectrometer alternatively a quadrupole mass filter has been employed.
  • a primary advantage of this quadrupole mass filter is its independency of the resolution power from the primary energy of the ions.
  • a further advantage results from the fact that the quadrupole mass filter is available as a compact and relative small unit, which facilitates its arrangement within the analyzing system.
  • the lines of the spectrum in FIG. 2 can be associated with certain types of ions and these again with certain compounds. This association may be carried out on the basis of known isotopic compositions, as in the case of C1, or by use of separately measured secondary ion spectra of certain compounds.
  • the spectrum represented in FIG. 2 shows that hydroxides, cyanides, chlorides, thiocyanates, nitrates, sulphates and the compounds of various carboxylic acids were present on the surface of the silver catalyst.
  • the process according to the invention is not limited in its application to the investigation of catalysts but can in principle be used successfully wherever problems of boundary surface physics or chemistry have to be investigated.
  • the process is also very suitable, for example, for the investigation of semi-conductor surfaces and semi-conductor boundary layers.
  • metal salt or oxide being present in the surface of the solid, and said analyzing comprises quantitatively analyzing the metal salt or oxide.
  • Apparatus for analyzing monolayers at the surfaces of solids comprising:
  • I connected in series to the open pulse multiplier, a pulse discriminator, a pulse forming device and an integrator.
  • the expanding means and the extracting means providing an extracted primary ion beam having a uniform current density of 10' to 10 amp. cmf resulting in a degradation time of 5 50 hours.

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  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Plasma & Fusion (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Analysing Materials By The Use Of Radiation (AREA)
  • Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
US00088747A 1969-11-14 1970-11-12 Process and apparatus for the mass spectrometric analysis of surfaces of solids Expired - Lifetime US3742227A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19691957311 DE1957311B2 (de) 1969-11-14 1969-11-14 Verfahren und vorrichtung zur massenspektrometirschen analyse von festkoerperoberflaechen

Publications (1)

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US3742227A true US3742227A (en) 1973-06-26

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US00088747A Expired - Lifetime US3742227A (en) 1969-11-14 1970-11-12 Process and apparatus for the mass spectrometric analysis of surfaces of solids

Country Status (8)

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US (1) US3742227A (de)
BE (1) BE758925A (de)
CH (1) CH522221A (de)
DE (1) DE1957311B2 (de)
FR (1) FR2069444A5 (de)
GB (1) GB1274580A (de)
IT (1) IT954075B (de)
NL (1) NL7016674A (de)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4163153A (en) * 1976-11-19 1979-07-31 Hitachi, Ltd. Ion beam means
US5401965A (en) * 1992-03-04 1995-03-28 Ebara Corporation Secondary ion mass spectrometer for analyzing positive and negative ions
DE19641981A1 (de) * 1996-10-11 1998-04-16 A Prof Dr Benninghoven Verfahren zur Bestimmung von Tiefenprofilen im Dünnschichtbereich
US5943548A (en) * 1996-07-02 1999-08-24 Samsung Electronics Co., Ltd. Method of analyzing a wafer in a semiconductor device fabrication process
US6576197B1 (en) * 1996-10-11 2003-06-10 Degussa Ag Method and device for revealing a catalytic activity by solid materials

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3128814A1 (de) * 1981-07-21 1983-02-10 Siemens AG, 1000 Berlin und 8000 München Elektrisch leitende probenhalterung fuer die analysentechnik der sekundaerionen-massenspektrometrie
JPS6044A (ja) * 1983-06-16 1985-01-05 Hitachi Ltd 二次イオン化質量分析装置
GB2269934B (en) * 1992-08-19 1996-03-27 Toshiba Cambridge Res Center Spectrometer

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2772363A (en) * 1952-03-21 1956-11-27 Cons Electrodynamics Corp Method and apparatus for ionization of solids
US3517191A (en) * 1965-10-11 1970-06-23 Helmut J Liebl Scanning ion microscope with magnetic sector lens to purify the primary ion beam

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2772363A (en) * 1952-03-21 1956-11-27 Cons Electrodynamics Corp Method and apparatus for ionization of solids
US3517191A (en) * 1965-10-11 1970-06-23 Helmut J Liebl Scanning ion microscope with magnetic sector lens to purify the primary ion beam

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Mass Spectrometric Micro Surface Analysis by Geophysics Corporation of America, Bedford, Mass. *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4163153A (en) * 1976-11-19 1979-07-31 Hitachi, Ltd. Ion beam means
US5401965A (en) * 1992-03-04 1995-03-28 Ebara Corporation Secondary ion mass spectrometer for analyzing positive and negative ions
US5943548A (en) * 1996-07-02 1999-08-24 Samsung Electronics Co., Ltd. Method of analyzing a wafer in a semiconductor device fabrication process
DE19641981A1 (de) * 1996-10-11 1998-04-16 A Prof Dr Benninghoven Verfahren zur Bestimmung von Tiefenprofilen im Dünnschichtbereich
DE19641981C2 (de) * 1996-10-11 2000-12-07 A Benninghoven Verfahren zur Bestimmung von Tiefenprofilen im Dünnschichtbereich
US6576197B1 (en) * 1996-10-11 2003-06-10 Degussa Ag Method and device for revealing a catalytic activity by solid materials

Also Published As

Publication number Publication date
NL7016674A (de) 1971-05-18
GB1274580A (en) 1972-05-17
CH522221A (de) 1972-06-15
DE1957311A1 (de) 1971-05-27
IT954075B (it) 1973-08-30
FR2069444A5 (de) 1971-09-03
BE758925A (fr) 1971-04-16
DE1957311B2 (de) 1972-10-12

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