《材料测试技术及方法》课程教学资源（书籍文献）Encyclopedia of Materials Characterization，PDF电子书，C. Richard Brundle，Surfaces, Interfaces, Thin Films

on Scatering Spectroscopy St.Paul,MN Allentown,PA Yale E.Strausse Auger Electron Spectroscopy stin,TX Neutron Diffraction X-Ray Diffraction Wojciech Vieth Glow-Discharge Mass Spectrometry William B.White Raman Spectroscopy 5.R.Wilson Optical Scatterometry w Mexic Variable Angle Spectroscopic Ellipsometry Lincoln.NE Ben G.Yacobi Cathodoluminescence Los Angeies.CA David J.C.Yates yd Chor or the Poway.CA Argonne,IL Contributors xix

Gene Sparrow Advanced R&D St. Paul, MN Fred A. Stevie AT&T Bell Laboratories Allentown, PA Yale E. Strausser Surface Science Laboratories Mountainview, CA Barry J. Streusand Applied Analytical Austin, TX Raymond G. Teller BP Research International Cleveland, OH Michael F. Toney IBM Almaden Research Center San Jose, CA Wojciech Viech Charles Evans & Assoociates Redwood City, CA William B. White Pennsylvania Skate UniVeI'Siq' University Park, PA S.R Wilson University of New Mexico Albuquerque, NM John A. Woollam University of Nebraska Lincoln, NE Ben G. Yacobi University of California at Los Angeles Los Angeles, CA David J. C. Yates Consultant Poway, CA Nestor J. Zaluzec Argonne National Laboratory Argonne, IL Ion Scattering Spectroscopy Surface Roughness: Measurement, Formation by Sputtering, Impact on Depth Profiling Auger Electron Spectroscopy Inductively Coupled Plasma Mass Spectrometry Neutron Diffraction X-Ray Diffraction Glow-Discharge Mass Spectrometry Raman Spectroscopy Optical Scatterometry Variable Angle Spectroscopic Ellipsometry Cathodoluminescence Physical and Chemical Adsorption for the Measurement of Solid Surface Areas Electron Energy-Loss Spectroscopy in the Transmission Electron Microscope Contributors xix

7 INTRODUCTION AND SUMMARIES 1.0 INTRODUCTION Though a wide range of analytical techniques is covered in this volume there are certain traits common to many of them.Most involve either electrons,photons,or ions as a probe beam striking the material to be analyzed.The beam interacts with the material in some way,and in some of the techniques the changes induced in the beam(energy,intensity,and angular distribution)are monitored after the inter- action, analytical inforr on is derived from the observation of these changes. In other techn ation ased for analysis omes from elec trons,photons,or ions that are ejected from the sample under the stimulation of the probe beam.In many situations several connected processes may be going on more or less simultaneously,with a particular analytical technique picking out only one aspect,e.g.,the extent of absorption of incident light,or the kinetic ange ofinfo atio but again ere are t山hemes What types of atio these techniques?Elemental composition is per aps the most ba followed by chemical state information,phase identification,and the determina- tion of structure(atomic sites,bond lengths,and angles).One might need to know how these vary as a function of depth into the material,or spatially across the mate- rial.and man techniques specialize in addressing thesequ estions down to very fine at all r surfa nd thin filr little m the pres cal s in this vol- ume.Within(m croanalysis)it ten necessa id ntify trace nents down to extremely lo number of techniques specialize in this aspect.In other cases a high rayin measuring the presence of major components might be theu.Usually accu the techniques that are good for trace identification are not the same ones used to accurately quantify major components.Most complete analyses require the use of 1

I INTRODUCTION AND SUMMARIES 1.0 INTRODUCTION Though a wide range of analytical techniques is covered in this volume there are certain traits common to many of them. Most involve either electrons, photons, or ions as a probe beam striking the material to be analyzed. The beam interacts with the material in some way, and in some of the techniques the changes induced in the beam (energy, intensity, and angular distribution) are monitored after the inter￾action, and analytical information is derived from the observation of these changes. In other techniques the information used for analysis comes from elec￾trons, photons, or ions that are ejected from the sample under the stimulation of the probe beam. In many situations several connected processes may be going on more or less simultaneously, with a particular analytical technique picking out only one aspect, e.g., the extent of absorption of incident light, or the kinetic energy distribution of ejected electrons. The range of information provided by the techniques discussed here is as0 wide, but again there are common themes. What types of information are provided by these techniques? Elemental composition is perhaps the most basic information, followed by chemical state information, phase identification, and the determina￾tion of structure (atomic sites, bond lengths, and angles). One might need to know how these vary as a function of depth into the material, or spatially across the mate￾rial, and many techniques specialize in addressing these questions down to very fine dimensions. For su&s, interfaces, and thin films there is ofien very little material at all to analyze, hence the presence of many microanalytical methods in this vol￾ume. Within this field (microanalysis) it is ob necessary to identify trace compo￾nents down to extremely low concentration (parts per trillion in some cases) and a number of techniques specialize in this aspect. In other cases a high degree of accu￾racy in measuring the presence of major components might be the issue. Usually the techniques that are good fbr trace identification are not the same ones used to accurately quantify major components. Most complete analyses require the use of 1

multiple techniques,the selection of which depends on the nature of the sample and the desired information. This first chapter contains one-page summaries of each of the 50 techniques cov ered in the following chapters.All su mmaries have the same format to allow easy compariso and quick a is pro vided in the intro d.cs to the infor ation.Furth er com ative i d at th end of this introduction,in which many of the important parameters describing the capabilities for all 50 techniques are listed. The subtitle of this Series is "Surfaces,Interfaces,and Thin Films."The defi- of sufaceor ofa"thinfim"varies coiderably from and with application The academic discipline of“S Scienc with emistry and physics at the atomic mono olayer lev whereas the "surface region"in an engineering or applications sense can be much more extensive.The same is true for interfaces between materials.The practical consideration in distinguishing "surface"from "bulk"or "thin"from "thick"is usually connected to the prope ty of interest in the application.Thus,for a cata- lytic the half a mo ay sulfur s in the catalyst ma erial might be crit wherea for a corro sion protection layer (for example,Cr segregation to the surface region in steels) the important region of depth may be several hundred A.For interfaces the epi taxial relationship between he last atomic layer of a single crystal material and the first layer of the adjoining material may be critical for the electrical proper- ties of a device sdiffusion barrier interfaces here in the may be 1000A thick.In thin-film om layers m thick,which for the majority of analytical tec iques discusse in this volum constitute bulk material,to layers as thin as 50 A or so in thin-film r orin Because ofthesdifrerofc and "thin,"actual numbers are used whenever discussing the depth an analytical tech- nique xamines.Thus in Ion Scattering Spectroscopy the sig nals used in the anal- are ge erated G the sed o vac reas in X-ray photoemi ssion up to 100 A is probed,and in X-ray orescence the signal can come from integrated depths ranging up to 10 um.Note that in these three examples,two are quoted as having ranges of depths.For many of the techniques it is impossible to assign unique values because the depth from which a signal originates may depend both on the particular manner in which the technique is used,and on the nature of the material being examined.Performing measurements at grazing angles of incidence of the probe or angles for the det ted si will usually m nake the tive X y, ion sc ttering is th rmore depythnm ctor in deter ng the pth a consis ng of ligh ments. 2 INTRODUCTION AND SUMMARIES Chapter 1

multiple techniques, the selection of which depends on the nature of the sample and the desired information. This first chapter contains onepage summaries of each of the 50 techniques cov￾ered in the following chapters. All summaries have the same format to allow easy comparison and quick access to the information. Further comparative information is provided in the introductions to the chapters. Finally, a table is provided at the end of this introduction, in which many of the important parameters describing the capabilities for all 50 techniques are listed. The subtitle of this Series is “Su&m, Interfices, and Thin Films.” The defi￾nition of a “surface” or of a “thin film” varies considerably hm person to person and with application area. The academic discipline of ‘‘Surfice Science” is largely concerned with chemistry and physics at the atomic monolayer level, whereas the “surface region” in an engineering or applications sense can be much more extensive. The same is true for interfaces between materials. The practical consideration in distinguishing “sudace” from “bulk” or “thin” from “thick” is usually connected to the property of interest in the application. Thus, fbr a cata￾lytic reaction the presence of haf a monolayer of extraneous sulfur atoms in the top atomic layer of the catalyst material might be critical, whereas for a corro￾sion protection layer (for example, Cr segregation to the surface region in steels) the important region of depth may be several hundred 8,. For interfaces the epi￾taxial relationship between he last atomic layer of a single crystal material and the first layer of the adjoining material may be critical for the electrical proper￾ties of a device, whereas diffusion barrier interfaces elsewhere in the same device may be 1000 A thick. In thin-film technology requirements can range from layers pm thick, which for the majority of analytical techniques discussed in this volume constitute bulk material, to layers as thin as 50 8, or so in thin-film magnetic recording technology. Because of these different perceptions of “thick” and “thin,” actual numbers are used whenever discussing the depth an analytical tech￾nique examines. Thus in Ion Scattering Spectroscopy the signals used in the anal￾ysis are generated fiom only the top atomic monolayer of material exposed to a vacuum, whereas in X-ray photoemission up to 100 8, is probed, and in X-ray flu￾orescence the signal can come from integrated depths ranging up to 10 pm. Note that in these three examples, two are quoted as having ranges of depths. For many of the techniques it is impossible to assign unique values because the depth from which a signal originates may depend both on the particular manner in which the technique is used, and on the nature of the material being examined. Perfbrming measurements at grazing angles of incidence of the probe beain, or grazing exit angles fbr the detected signal, will usually make the technique more surface sensi￾tive. For techniques where X-ray, electron, or high-energy ion scattering is the critical Factor in determining the depth analyzed, materials consisting of light elements are always probed more deeply than materials consisting of heavy ele￾ments. 2 INTRODUCTION AND SUMMARIES Chapter 1

Another confusing issue is that of "depth resolution."It is a measurement of the technique's ability to clearly distinguish a property as a function of depth.For m that th one depth can be distinguished fr that at ano he depth if there is veen them. A depth profile is a record of the variation of a property(such as composition)as a function of depth.Some of the techniques in this volume have essentially no intrinsic depth profiling capabilities;the signal is representative of the material inte- grared over fixed probing depth.Most.however,cn vary the depth probed by nalysis,or by removing the surface,layer by ecting data By varying the angle of incidence,the X-ray,electron,or ion beam energy,etc. many techniques are capable of acquiring depth profiles.Those profiles are gener- ated by combining several measurements,each representative of a different inte- ion scattering techniques (Medium Energy Ion ing,MEIS,and Ruthe atter RBS)h eve that the natural output of th s is compo of depth.Byf the most common way of depth profiling is the destructive method of removing th surface,layer by layer,while also taking data.For the mass spectrometry-based techniques of Chapter 10,removal of surface material is intrinsic to the sputtering and ionization pro cess.Othe r methods,such as Auger Electron Spectroso y,AES or X-Ray Ph ssion ,XPS,use an ial while const ntly ionizing the newly expos surface. he most vorable condi- tions depth resolutions of around 20 A can be achieved this way,but there are many artifacts to be aware of and the depth resolution usually degrades rapidly with depth.Some aspects of sputter depth profiling are touched upon in the article"Sur- face roughness"in chap pter 12,but for a more complete discussion of the capabil- ities and limitations of is referred to nd Fine., cited there

Another confusing issue is that of “depth resolution.” It is a measurement of the technique’s ability to clearly distinguish a property as a function of depth. For example a depth resolution of 20 A, quoted in an elemental composition analysis, means that the composition at one depth can be distinguished from that at another depth if there is at least 20 A depth profile is a record of the variation of a property (such as composition) as a function of depth. Some of the techniques in this volume have essentially no intrinsic depth profiling capabilities; the signal is representative of the material inte￾grated over a fived probing depth. Most, however, can vary the depth probed by varying the condition of analysis, or by removing the surface, layer by layer, while collecting data. By varying the angle of incidence, the X-ray, electron, or ion beam energy, etc. many techniques are capable of acquiring depth profiles. Those profiles are gener￾ated by combining several measurements, each representative of a different inte￾grated depth. The higher energy ion scattering techniques (Medium Energy Ion Scattering, MEIS , and Rutherford Backscattering, RBS), however, are unique in that the natural output of the methods is composition as a function of depth. By far the most common way of depth profiling is the destructive method of removing the surface, layer by layer, while also taking data. For the mass spectrometry-based techniques of Chapter 10, removal of surface material is intrinsic to the sputtering and ionization process. Other methods, such as Auger Electron Spectroscopy, AES, or X-Ray Photoemission, XPS, use an ancillary ion beam to remove material while constantly ionizing the newly exposed surface. Under the most favorable condi￾tions depth resolutions of around 20 A can be achieved this way, but there are many artifacts to be aware of and the depth resolution usually degrades rapidly with depth. Some aspects of sputter depth profiling are touched upon in the article “Sur￾face Roughness” in Chapter 12, but for a more complete discussion of the capabil￾ities and limitations of sputter depth profiling the reader is referred to a paper by D. Marton and J. Fine in Thin Solid Films, 185, 79, 1990 and to other articles cited there. between them. 3

Compilation of Comparative Information on the Analytical Techniques Discussed in This Volume Depth Technique probed Types of solid sample pro (typical) (typical) 2.1 Light Microscopy Variable 0.2m A 1 SEM subμm 10 nm Cond.,coated ins. 2 Y 2 STM sub A 1A 二 Conductors N SFM I nm All 2 32 24 TEM 200nm 5 nm All;<200 nm thick Y 3 YYYY 2 EDS 1m 0.5μm 500 ppm All;Z>5 Y EELS 20nm* 1nm Few All;<30 nm thick 2 223 33 Cathodo- 10nm-μm 1 um Ppm All;semicond.usually Y 1 luminescence 3 N NTRODUCTIONS AND SUMMARIES STEM 100nm I nm All;<200 nm thick Y 3 3 EPMA 14m 0.54m 100 ppm All;flat best Y 3 2 XRD 10m mm 3% Crystalline Z>> N EXAFS Bulk* mm Few Y/ SEXAFS 1 nm mm Few Surface and adsorbate NEXAFS mm Few Surface and adsorbate Y 2- 13 33 N 4.4 XPD 3 nm 150μnm 19% Single crystal Y LEED 】nm 0.1 mm Single crystal RHEED 1 am 0.02mm Single crystal XPS 3 nm 150um 一% All Chapter 5.2 UPS 1 nm All YYYY mm 3-33 322131 ZZZZ 5.3 AES 2 nm 100nm 0.1% All,inorganic usually

Compilation of Comparative Information on the Analytical Techniques Discussed in This Volume Main information Article Technique No. 2.1 2.2 2.3 2.3 2.4 3.1 3.2 XI 0 3.3 0 3.4 C 0 z 4.1 rn P 4.2 0 4.3 C 4.3 4.4 5E !E Fi rn 4.6 3 2 3.5 v) % 4.5 5.1 5.2 5.3 8 PI R 4 d Light Microscopy SEM STM SFM TEM EDS EELS Gthodo- 1 u m i n & ce n ce STEM EPMA XRD EXAFS SEXAFS NEXAFS XPD LEED WEED XPS UPS AES Depth probed (wid) Variable me sub pm mmm sub A mem sub A 200 nm* 1pm me e 20 nm* eeme e .e 10 nm-pm 100 nm* e lpm 10 Cun e e Bulk* e e lnm e. e. e. 1 nm m. 3nm 1 nm mm lnm me 3nm me e 1 nm e. 2 nm Tp of solid sample (typical) 0.2 pn 10 nm iA 1Ml 5 nm 0.5 pn 1 nm 1Cun lnm 0.5 pm mm mm mm mm 150 prn 0.1 mrn 0.02 mm 150 pm mm 100 nrn 500 ppm Few% PPm - 100 ppm 3% Few % Few % Few% 1% - - 1% 0.1% - All Cond, coated ins. Conductors All All; e200 nm thick AU; Z> 5 All; e30 nm thick All; sunicond. usually All; e200 nm thick All; flat best Crystalline All Surface and adsorbate Surface and adsorbate Single crystal Single crystal Single crysml All All All, inorganic usually N1 Y2 N2 N2 Y3 Y2 Y2 Y1 Y3 Y3 N2 YIN - Y- Y- Y3 Y- Y- Y3 Y- Y3 1Y 1Y 3Y 2Y 2Y 2Y 3N 3N 3N 2Y 1Y 3N 3N 3N 3N 2N 2N 1Y 3N 1Y