INTRODUCTION This work incorporates the results of 41 years experience in ion implantation (1964-2004) and 36 years in secondary ion mass spectrometry (SIMS) (1969-2004). These two technologies became intertwined when the need became apparent for the measurement of depth profiles of elements implanted into many materials under many conditions during and after implantation, for which SIMS was ideally suited, and the realization that while SIMS was a powerful tool for this, SIMS required accurate calibration for the many elements in the many materials, for which ion implantation offered a versatile solution. During 1968, Charles A. Evans, Jr. and I set out to meet these reciprocal needs, and in April of 1959, I began a long series of trips between Malibu CA (then Hughes Research Laboratories) and the San Francisco Bay area where Charles Evans and Associates had several laborator locations during the next 35 years. Some years later, Fred A. Stevie joined this collaboration and between us implants of 83 elements into Si were studied, and 76 elements were implanted into other materials, especially GaAs. About 60 materials were implanted and studied using SIMS during these years. In 1974, George brewer and I published a book (John Wiley) on ion beams and ion implantation, and in 1989, Fred Stevie, Charles Magee, and I published a book on SIMS (Wiley Interscience). The latter book deals primarily with SIMS of semiconductors. This present work adds metals, insulators, (conductors), insulators (dielectrics), wide bandgap materials, and polymers, to this list of substrate materials. These additions broaden substantially the materials list for which the techniques described in Wilson, Stevie, and Magee (WSM) have been applied. Si and the other semiconductor materials studied in WSM are included here for comparison and completeness; some new data, especially actual figures are included here. The total list now includes: Metals (conductors): Be, Al, Ti, TiN, TiSi2, Ni, Cu, W, Au Insulators (dielectrics): SiO2, Si3N4, Al2O3, LiNbO3, UO2 Semiconductors: SI, Ge, GaP, GaAs, GaSb, InP, InAs, InSb, HgCdTe Wide Bandgap materials: diamond (C), SiC, GaN, ZnSe, ZnS Polymers: epoxy, polymethylmethacralate/PMMA/Lucite/AZ111, polypromellitimide/polyimide/Kapton ACKNOWLEDGMENTS – PEOPLE, ORGANIZATIONS, SUPPORT Throughout these 41 years, various people and organizations have helped or supported this work in various ways. Significant financial support via Independent Research and Development funds (IRD) within Hughes Aircraft Company at Hughes Research Laboratories. The associated amount of money can only be roughly estimated, but if we assume about 100K$ per year for 25 years, the amount is of the order of 2.5M$. Significant financial support was provides via IRD and internal funding within Charles Evans and Associates during the years 1969-1998. If we assume 30K$ per year for 20 years, the amount is about 600K$. Significant financial support was provided via the federal government, especially the DoD and the Army Research Office in particular. See the list of government contracts given at the end of this section. Persons who have contributed to or supported in some way this work include: George R. Brewer HRL, my close associate and supporter at HRL, without whom this would not have happened. Thanks, George Robert Bower HAC James Comas NRL Harry Dietrich NRL John Davies Chalk River Nuclear Laboratories Vaughn Deline CEA Fred Eisen Rockwell Science center James Ehrstein NBS -> NIST Charles A. Evans, Jr. CEA, my friend and supporter, without whom this would not have happened. Thanks, Drew James Gibbons Stanford University Ken Galloway NBS -> NIST Charles Hitzman CEA Harold Hughes NRL Douglas Jamba HRL, my associate in the lab in Malibu for 25 years, without whom this would not have happened. Thanks, Doug Ogden Marsh HRL James Mayer HRL -> ASU Steven Novak CEA Douglas Phinney Lawrence Livermore Laboratory. Thanks, Doug for your support Steven J, Pearton Univ. Florida Thanks, Steve for your support Devendra Sadana UC Berkeley Steve Smith CEA Fred A. Stevie BTL -> Lucent -> NCSU, without whom much of this would not have happened. Thanks, Fred Edward Wolf HRL -> Cornell U. Max Yoder NRL John Zavada ARO, without whom this would not have happened. Thanks, John for your support in many ways for so long a time. My wife, Billie, without whom this would not have happened. Financial support was provided via various government contracts, as follows: Gov’t Contract No. Program Title Dates Agency NASA NAS-3-5249 Electrode surface physics research 1963-Jun1965 NASA NAS 3-5278 Ion thruster surface physic studies/ Jun1965Jun1967 Work function & adsorption energy calcs. AFAL AF33(616)=3821 Ion implantation doping techniques Oct1966Oct1968 ONR /N00014-69-C-0171 Selective doping of piezoelectric NASC crystals by ion implantation AFML F33615-70-C-1238 Manufacturing methods for ion implanted Sep1970Sep1972 MOSFET devices and circuits NARAIR N00019-69-C-0691 Beam techniques for the fabrication of Sep1969Sep1970 Microwave integrated circuits N00019-72-C-0364 with R.L. Seliger Jan1972-Jan1973 N00019-73-C-0261 Jan1973-Mar1974 NESC N00039-73-C-0059 Integrated Circuit and Manufacturing May1973Nov1973 Science and Technology (ICRMS) NOSC N00123-73-C-1081 Fabrication techniques for integrated Sep1972Feb1973 Optical circuitry NOSC/ N00123-75-C-0080 SOS isolation techniques Oct1974Aug1975 NRL DARPA/DoC 5-35891 Critical implantation parameters Apr1975-Jun1980 DARPA/ N00014-81-C-0286 Implantation damage and regrowth Feb1981Feb1982 ONR DARPA/ MDA-903-83-C-0108 Channeling in IR detector materials Jun1982-Mar1986 SBRC Part of HgCdTe surface and defect study program SBRC ARO DAAL03-86-C-0010 Secondary ion mass spectrometry Apr1986Dec1989 C. Evans and Assoc. char. Of implants into GaAs and InP for waveguides and integrated optics NRL/ N0014-87-C-2389 Materials improvement techniques and Sep1987Nov1989 DNA diagnostics of SIMOX structures NOSC N6601-89-M BH18 Implantation of diamond substrates May1989Oct1990 anneals, SIMS, metallizations ARO DAAL03-91-C-0001 Modification and characterization of Apr1991Apr1994 II-VI and III-V materials using ion beams Martin Marietta Device Implantation 1993-1996 ATM contract Diamond implantation 1994 ARO DAAH04-95-C-0043 Electro-optics based on novel materials Jun1995Jun1998 modification DARPA ?? Diamond thermal management HSC/RSC Oct1997Oct1999 ARO DAAG55-98-C-0045 Electro-optics based on novel materials Jul1998Jun2001 Modification ARO DAA?? ??? Univ. Florida Sep2002Aug2005 WHAT INFORMATION IS IN THIS WORK Resources for SIMS and Ion Implantation Technologies New SIMS RSF data and ion implantation ranges and depth profiles for most elements in metals (Be, Al, Ti, Ni, Cu, W, and Au) New SIMS RSF data and ion implantation ranges and depth profiles for most elements in insulators (dielectrics) (SiO2, Si3N4, Al2O3, LiNbO3, UO2) New SIMS RSF data and ion implantation ranges and depth profiles for most elements in wide bandgap materials (diamond (C), SiC, GaN, ZnSe,SnS) New SIMS RSF dat and ion implantation ranges and depth profiles for most lements in polymers (epoxy, PMMA, polyimide) Measurement of electronic stopping powers for most elements in Si via measurement of the maximum channeling range in the <110> direction of Si and some GaAs Measurement of the solid state and stoichiometric electron affinities of most of the elements in Si and some GaAs via SIMS measurements Some special features of this work include the results of studies or techniques described below: References to early work and early papers – 1963 to ~1988 Correlation between implantation damage/depth distributions and mobile impurity depth distributions measured using SIMS and TEM for implanted Cr, Cu, Ag SIMS mass spectra for many different kinds of materials Shapes of deep <110> channeling profiles for nearly all elements channeled in Si FIB (focused ion beam) depth profiles compared with random and channeled Implantation profiles Shallow vs deep implantation profiles and effect on SIMS RSFs for B, Ga, and As A history of early ion implantation, including conferences, patents, news releases ook, reviews, and papers A history of early implanters C-V and Pearson IV profile techniques Ion beam mass analysis for implanter ion beams SIMS for molecular ions SIMS for multiple implants MeV implantation and channeling Amorphous vs crystalline implanted depth distributions Experimentally measured moments of implanted depth distributions determined using a Pearson IV fitting routine Comparison of experimental ranges with calculated ranges uding TRIM and ISPC Extended studies of implantation of Si and As including MeV energies SIMS quantification Cs molecular SIMS DEFINITIONS WSM represents Wilson, Stevie, and Magee, Secondary Ion Mass Spectrometry [Wiley, New York, 1989] E is often used to represent element, O to represent oxygen, and M to represent matrix, etc. when secondary ions are discussed SIMS represents secondary ion mass spectrometry RSF represents (SIMS) relative sensitivity factor, the calibration factor to convert secondary ion signal (counts/sec) to atom density (cm-3), via the matrix signal measured under identical instrument conditions wrt represents with respect to Ion Implantation Ion implantation is a versatile process that can introduce any element into any solid material to any density under nonequilibrium conditions, irrespective of solid solubility, at any temperature compatible with the material, and at depths that depend on the energy capability of the equipment. The resulting damage to crystals is an issue and annealing is used to remove as much of that damage as is compatible with the temperatre limitations of that material. Elements can be introduced in to materials using ion implantation that may alter the electrical, optical, mechanical, magnetic or other properties of the material. Implantation is a major technique used in the Si device and circuit industry for doping and other processing steps; it is used less in III-V materials and device technologies and very little in narrow bandgap II-Vi technologies because it is difficult to remove the damage (point defects and various extended defect complexes) created by the energetic energy loss processes that occur as the ions come to rest in crystalline materials, because of temperature limitations of those material. High temperature materials are better candidates for implantation processing , materials that include GaN. There are many previous s and books about ion implantation, damage, and annealing. See the references in this work. SIMS Secondary ion mass spectrometry (SIMS) is a surface analytical technique that is ideally suited to measuring depth profiles of implanted and annealed materials. Effects of annealing on the depth distributions of implanted species, unintentional impurities, and the elements of substrate (matrix) materials themselves can be measured using SIMS. SIMS analyses can be quantified accurately by using implanted standards of accurately know fluence. Figure 1 illustrates such a quantification standard for K implanted in Si. A quantification measure for SIMS called the relative sensitivity factor (RSF) is established by setting the integral under the measured depth distribution equal to the accurately measured fluence of the implant [time integral of the current density (adjusted for the charge on the ion)]. This RSF can then be used at any later time to quantify impurity densities by measuring the ratio of the intensity of the secondary impurity ions to the intensity of the same matrix ion for which the RSF was measured1 – for instruments that have time consistent properties, the matrix being one of the elements in any selected material . Annealing and associated terminology Annealing is a process often used with ion implantation – to reduce or remove the damage or effects of damage caused in implanted crystalline materials during the energy loss of energetic ions. In amorphous materials, damage has little meaning because the atoms or molecules have little or no organized physical relative location. Our Webster’s dictionary give four sub-definitions for the word “anneal,” all four of which use temperature (elevated) in the definition. Therefore “thermal anneal” is redundant; the word thermal is totally unnecessary. “Anneal” or “annealing” requires elevated temperature. Therefore, we use “rapid anneal” here to describe short-time annealing rather than the redundant term, often seen in the literature, rapid thermal annealing or RTA. The term RTP or rapid thermal processing does not suffer from this criticism, so it is used here. The common alternative to rapid annealing is furnace annealing. Rapid annealing is often done using flash lamps of a variety of types. Range Parameters Terminology A discrepancy has occurred historically in the literature in the use of symbols regarding the range parameters used in ion implantation, as follows: Originally Rp was used for the most probable range, and Rm was used for the mean (median?) range. Later Rp was used for the projected range (from LSS), or the first moment, , and Rm was used for the range mode, or most probable range, or the depth of the peak of the depth distribution or profile. Rp was then used for the range straggle or second moment, . We use these latter definitions in this work. The third central moment is then 1, and the fourth central moment is 2. Random Equivalent Terminology We use the term random orientation or random equivalent orientation as we first heard it used, namely as any one of several orientations that produce the average Rutherford backscattering signal that occusr between channeling dips [excluding the higher signal shoulders (quasichanneling) that occur just before the dips]. One early orientation that was believed to fulfill thios criterion was 7 or 8 degrees tilt ans 18 degrees azimuthal rotation or “twist.” That is, 8 degrees tilt from the condition where the beam direction is normal to the surface target surface and 18 degrees rotation of a flat from the line through the target (wafer) about which the 8 degree tilt was made. For a <100> Si wafer, there are four <110> flats, for example. This is a historical definition; more recent experimental studies may have improved upon the definition. Another random condition was the <763> used by Hofker in 1975. When the ion velocity becomes small ( the ion energy is small and/or the ion mass is large), the critical angle for channeling becomes large, to the order of 5 degrees, and the tilt angle may better be increased to 10 degrees (or even larger). There is a publication that indicates that the practical tilt angle should be twice the classical Lindhard critical angle for channeling, in order to minimize unintentional channeling during implantation [NBS Special Publication 400-49, 197]. There is a body of literature in which the issue of tilt angle and the need for an angle larger than 7 degrees is discussed for Si implants into GaAs.