Method and apparatus for investigating the physical properties of material surface layer

Abstract: An improved method is disclosed which investigates the surface layer of a material. A pulsed slow positron beam (1) having a pulse duration in a nanosecond range is focused and irradiated on the reverse surface of a thin-film-like sample (2), and a probe (3) is brought into contact with the front surface of the sample. Surface positrons are swarmed in a gap space at the contact point so as to form positronium molecules Ps n (n is an integer equal to or greater than 2). Coherent annihilation gamma-rays generated due to annihilation of the positronium molecules Ps n are detected so as to discriminate the positronium molecules Ps n from positrons and positroniums Ps, thereby measuring on an atomic scale the physical properties of the surface layer of the material with a response time shorter than 1 nanosecond. This method makes it possible to measure on an atomic scale the state of local electrons at a surface layer of a material and activities at the surface layer, such as catalytic activity, with a response time shorter than 1 nanosecond.

Description: BACKGROUND OF THE INVENTION Field of the Invention: The present invention relates to a method and apparatus for investigating on an atomic scale not only the state of local electrons but also catalytic activity and other activities at the surface layer of a new material or the like, with a response time shorter than one nanosecond. Description of the Related Art: Observation of positron annihilation gamma-rays, which is very effective in the investigation of bulk crystals or the like has provided important information on the state of local electrons inside or at the surface of a sample, which are averaged in terms of time and space. However, since there has been no method of determining on an atomic scale the location where a positron annihilation gamma-ray is generated, it has been impossible to investigate microscopically activities such as catalytic activity at the surface layer of a sample. Therefore, there has been a problem that the activities such as catalytic activity at the surface layer or at an interface of a material cannot be investigated on an atomic scale with a response time shorter than 1 nanosecond. JP-A-5 010 895 discloses apparatus for inspecting the surface physical properties of a sample in which a low speed positron beam is focused thereonto. A probe (7) adjacent the surface of the sample defines a space in which the positrons gather to form positronium. Annihilation of a resulting positronium cluster Ps n generates two gamma rays whose energies are sorted to provide detection of the positronium. SUMMARY OF THE INVENTION An object of the present invention is to solve the above-described problems and to provide an improved method and apparatus for investigating on an atomic scale the physical properties of a surface layer of a material, thereby making it possible to observe on an atomic scale the state of local electrons and activities such as catalytic activity at the surface layer or at an interface of a sample, with a response time shorter than 1 nanosecond. In order to achieve the above object, according to the present invention: (1) positronium molecules Ps n are used as a probe which allows high sensitivity measurement of the physical properties of a material surface layer, in particular, activities such as catalytic activity with high sensitivity; (2) in order to selectively detect a positronium molecule Ps n , there is used a coherent annihilation gamma-ray that is generated due to coherent photon annihilation in which all positroniums Ps that constitute the positronium molecule Ps n simultaneously annihilate in the same phase; and (3) there is changed on an atomic scale the location where a positronium molecule Ps n is formed for the atomic scale investigation of the activity of the material surface layer. BRIEF DESCRIPTION OF THE DRAWING FIG. 1 shows a schematic layout diagram of a scanning positronium-molecular microscope according to an embodiment of the present invention in which pulses of a slow positron beam have an energy of a few keV to a few tens of keV and a duration in the nanosecond range. DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will now be described below in detail. (1) Positronium molecules Ps n serve as an ideal probe that makes it possible to observe, on an atomic scale, activities at a material surface layer. The positronium molecule Ps n is a molecule composed of n positroniums Ps, which are the lightest atoms, and consists of n positrons and n electrons. Among the positronium molecules Ps n , a positronium molecule whose degree of clustering n is 2 is called dipositronium and is the lightest molecule in the universe. (2) The possibility of the presence of the dipositronium Ps 2 was pointed out a half century ago (see "E. A. Hylleraas and A. Ore, Phys. Rev. 71 , 493 (1947)"). Since then, many theoretical studies have been conducted regarding the shape and binding energy of the dipositronium Ps 2 . However, since no method of detecting the dipositronium is known, the dipositronium has not yet been observed. (3) The shape and binding energy of a stable dipositronium Ps 2 can be determined through use of the condition for minimizing the internal energy of the dipositronium Ps 2 that is the sum of the zero-point energy; i.e., the kinetic energy and the potential energy. Here, the kinetic energy is obtained through quantization of each angular momentum for the respective three orthogonal axis passing through the center of mass of Ps 2 into h/π, where h is Planck's constant. (4) The thus-obtained results are in good agreement with the numerical solutions obtained through computer calculations reported to date. The results can be summarized as follows. (a) In a dipositronium Ps 2 isolated in vacuum, two p-Ps (para positroniums) or two o-Ps (ortho positroniums) are coupled with each other with a weak binding energy B given by the following relation:. B = 2E(Ps)-E(Ps 2 ) ≒ 0.4 eV, wherein E(Ps) is the total energy of Ps, and E(Ps 2 ) is the total energy of Ps 2 . Therefore, Ps 2 is stable only at the ground state. (b) The dipositronium Ps 2 has a shape similar to a regular tetrahedron or pyramid-like shape in which each side has a length of: r ev ≧ r od ≒ 6 a o = 3.2 Å = 0.32 nm, wherein r ev and r od are mean spacings between the nearest neighbors with the same sign of charge and those of opposite sign of charge, respectively, and a o is the Bohr radius. (c) Due to the very small binding energy B, the electron density n(Ps 2 ) within Ps 2 , or the density of electrons at the position of the positron, becomes almost the same as the electron density n(Ps) within Ps. Therefore, the annihilation rates of p-Ps and o-Ps within Ps 2 are in proportion to n(Ps 2 ) and are respectively the same as those of isolated p-Ps and o-Ps except the statistical factors. The particularly important result is that the spacing between two Ps within Ps 2 is shorter than the deBroglie wavelength, so therefore they are coherent, i.e., in the same phase like the Bose-Einstein condensation. Since Ps is a basic ionic-bond atom, the above consideration on the configuration of Ps 2 can be applied to Ps n , where n > 2. Therefore, in the decay mode of Ps n , in addition to the two-photon annihilation rate λ(Ps n → 2γ, Ps n-1 ) which represents the probability at which each Ps within Ps n annihilates independently, there must be considered the coherent 2n-photon annihilation rate λ(Ps n → 2nγ) which represents the probability at which positroniums Ps in a number of n simultaneously annihilate yielding n coherent photon pairs in the same directions. (5) The probability λ(Ps n → 2γ, Ps n-1 ) at which any one of the positroniums Ps within a positronium molecule Ps n is n times the annihilation rate of an individual Ps is represented by the following equation: λ(Ps n → 2γ, Ps n-1 ) = nλ(Ps → 2γ) When n positroniums Ps cause coherent photon annihilation in the same phase, the amplitude of annihilation instead of probability becomes n times that of a single positronium; therefore the probability is represented by the following equation: λ(Ps n → 2nγ) = n 2 λ(Ps → 2γ), or λ(Ps n → 2nγ) = nλ(Ps n → 2γ, Ps n-1 ). This leads to the conclusion that more than half of the positronium molecules Ps n cause coherent annihilation. In coherent annihilation, n pairs of photons are radiated at the same time and in the same directions. Therefore, when such coherent annihilation is observed through use of an ordinary gamma-ray detector, the coherent annihilation is detected as if it were a two-photon annihilation having an energy of n x 511 keV; i.e., n times the energy of an annihilation gamma ray. (6) From the above consideration, it is found that through measurement of the spectrum distribution of a annihilation gamma ray, the degree of clustering n of a positronium molecule Ps n is determined from the energy of the gamma ray, and the formation rate of Ps n can be determined based on the spectrum intensity distribution of the gamma ray. Next, with reference to FIG. 1, a description will be given of an embodiment in which positronium molecules Ps n serving as a probe are utilized so as to investigate on an atomic scale the physical properties of the surface layer of a material, in particular, activities such as catalytic activity. FIG. 1 shows a schematic layout diagram of a scanning positronium-molecular microscope according to an embodiment of the present invention in which pulses of a slow positron beam have an energy of a few keV to a few tens of keV and a duration time in the nanosecond range. In FIG. 1, numeral 1 denotes a slow positron beam, numeral 2 denotes a thin film sample, numeral 3 denotes a probe, numeral 4 denotes a coherent annihilation photon pair, numeral 5 denotes an annihilation gamma ray (photon) detector, numeral 6 denotes a radiation shield, numeral 7 denotes a positron beam focusing electrode system, numeral 8 denotes a solenoid coil, and numeral 9 denotes a coincidence annihilation gamma-ray spectrum analyzer. The thickness of the thin film sample 2 is set to approximately 0.1 µm so as to allow the slow positron beam 1 to pass through the sample 2. The slow positron beam 1 is irradiated onto the reverse surface of the sample 2 such that it converges on the reverse surface. At the convergence point, the beam 1 has a diameter corresponding to the thickness of the sample 2. A considerable portion of the irradiated positrons swarm at the front and reverse surface of the thin film sample 2 in the form of surface positrons. Surface positrons refer to thermal positrons which are bound to the surface by their image potential. When the potential difference between the probe 3 and the thin film sample 2 is properly adjusted, the surface positrons swarm in a very small gap space between the tip of the probe 3 and the thin film sample 2, so that the positrons are coupled with electrons to form positroniums Ps and positronium molecules Ps n . The rate Z(Ps) of positronium Ps formation at the surface can be obtained on the basis of thermodynamics. That is, the positronium formation rate Z(Ps) is obtained in accordance with the following equation: Z(Ps) = (hm o n o /2πm + 2 )(1-r 1 )exp(-E a /kT) wherein m o is the mass of an electron, m + is the effective mass of a surface positron, E a is the mean energy with which the positronium Ps is bound to the sample surface, k is Boltzmann's constant, T is the temperature of the surface layer of the sample, r 1 is an average value of the reflection coefficient of the positronium Ps at the sample surface, and n o is the critical density of the surface positrons. The critical density n o of the surface positrons is given by the following expression: n o = 8π 2 m + kT/h 2 . At the surface layer of the material, a dipositronium Ps 2 is formed through interaction between two surface positrons. The thermodynamically-obtained formation rate (Ps 2 ) is expressed as follows: Z(Ps 2 ) = (hm o n + /2πm + 2 )(1-r 2 )exp(B-2E a /kT) wherein r 2 is an average value of the reflection coefficient of the dipositronium Ps 2 at the sample surface, and n + is the density of surface positrons. The value of B, which represents the binding energy of the positroniums Ps within the dipositronium Ps 2 , may slightly deviate from the value of Equation (1) depending on the state of the surface layer. From Equations (7) and (8), the formation ratio between Ps and Ps 2 synthesized at the surface layer of the material becomes as follows: Z(Ps 2 )/Z(Ps) = (n + /n o )(1-r 2 /1-r 1 )exp[(B-E a )/kT] Since the value of E a varies depending on the surface treatment of the sample, the formation ratio varies sensitively with the condition of the surface layer of the sample; such as chemical activity through exponential dependence on (B-E a ). For example, in the case where surface positrons of n + ≒ 10 5 cm -2 swarm around the tip of the probe at the surface layer of r 1 ≒ r 2 and E a ≒ 0.1 eV, at temperatures below the freezing point, the formation of dipositronium Ps 2 of B ≒ 0.4 eV drastically increases with a decrease in temperature. At the temperature of liquid nitrogen, more dipositroniums Ps 2 than positroniums Ps are formed. Needless to say, the above-described discussion regarding the dipositroniums Ps 2 can be applied to positronium molecules having a larger degree of clustering of positroniums (n>2). The formation of the positronium molecules Ps n is greatly affected by absorbed molecules on the surface of the sample, and by the state of the outermost layer such as fine defects, as well as by the local densities of the surface positrons and electrons at the surface. Accordingly, adjustment of very small potential difference between the probe 3 and the thin film sample 2 makes it possible to change the density of the surface positrons so as to change the formation rate of the positronium molecules Ps n and the spectrum of the degree of clustering n. The time dependence of the formation rate and the degree of clustering of the positronium molecules Ps n can be investigated by changing the intensity and pulse duration of the slow positron beam 1. The molecular axes of the positronium molecule Ps n formed at the surface layer of the sample; i.e., the axes that connect the centers of the components Ps within the Ps n are parallel to the surface layer of the sample, because the image potential which traps the positronium molecule Ps n at the surface layer is planar. Since coherent annihilation photon pairs 4 are generally radiated along the molecular axes in opposite directions, the coherent annihilation photon pairs 4 of the positronium molecules Ps n formed at the surface layer of the sample are radiated in only directions parallel to the surface layer, so that the detection efficiency can be greatly gained through arrangement of the detector as shown in FIG. 1, as compared to an ordinary arrangement in which annihilation photon pairs are uniformly radiated into space. Since positronium molecules Ps n are formed in a very small space and the positronium molecules Ps n formed are selectively detected at high efficiency, it is easy to trace the formation point while changing it on an atomic scale through super-microdrive, i.e., piezodrive of the probe. Therefore, it becomes possible to investigate variations with time and spatial distribution of the activities of the outermost layer of the sample. This becomes a powerful means for developing new materials. The slow positron beam 1 is repeatedly irradiated to provide pulses each having a duration of 1 nanosecond or less. This makes it possible to measure tunneling current that flows through the probe during a period between the pulses. Accordingly, in addition to the function for observing positronium molecules Ps n , the apparatus of the present invention can have a function of serving as a scanning probe microscope of a different type such as a scanning tunneling microscope, so that various kinds of information can be obtained simultaneously on an atomic scale. The present invention is not limited to the embodiments described above. Numerous modifications and variations of the present invention are possible within the scope of the invention according to the appended claims. For example, the slow positron beam may be irradiated onto the front surface of the sample with which the probe is contacted. The present invention provides the following advantages: (A) A pulsed slow positron beam having a pulse duration in a nanosecond range is focused and irradiated on the reverse surface of a thin-film-like sample of a material, a probe is brought into contact with the front surface of the sample such that the probe faces the irradiated slow positron beam. The probe is driven in the same manner as in a scanning tunneling microscope. Surface positrons are swarmed in a gap space at the contact point so as to form positronium molecules Ps n , and coherent annihilation gamma-rays generated due to annihilation of the positronium molecules are detected, thereby selectively observing the Ps n . Subsequently, the intensity of the coherent annihilation gamma-rays is compared with the intensity of other positron annihilation gamma-rays, so that it becomes possible to measure on an atomic scale the physical properties of the outermost layer of a material, in particular, activities such as catalytic activity, with a response time shorter than 1 nanosecond. (B) Since the scanning positronium-molecular microscope can have a function of serving as a scanning probe microscope of a different kind, variety kinds of information can be obtained on an atomic scale.

Claims: A method of investigating the surface layer of a material, characterized in that a pulsed slow positron beam (1) having a pulse duration in a nanosecond range is focused and irradiated on the reverse surface of a thin-film-like sample (2) of the material, a movable probe (3) is brought into contact with the front surface of the sample such that the probe faces the focused slow positron beam, surface positrons are swarmed in a gap space at the contact point so as to form positronium molecules Ps n (n is an integer equal to or greater than 2), and coherent annihilation gamma-rays generated due to annihilation of the positronium molecules Ps n are detected so as to discriminate the positronium molecules Ps n from positrons and positroniums Ps, thereby measuring on an atomic scale the dynamical properties of the surface layer of the material with a response time shorter than 1 nanosecond. A method of investigating the surface layer of a material according to Claim 1, characterized in that the location of formation of positronium molecules Ps n is moved on an atomic scale by changing the position of the probe, and the spectrum of coherent annihilation gamma-rays generated due to annihilation of the positronium molecules Ps n is measured through scanning observation so as to determine the location and duration of formation of the positronium molecule Ps n as well as the degree of clustering n of the positronium molecule Ps n , thereby measuring the activity of the surface layer of the material on an atomic scale. A scanning positronium-molecular microscope, characterized by comprising: (a) means for focusing and irradiating, on the reverse surface of a thin-film-like sample of a material, a pulsed slow positron beam having a pulse duration in a nanosecond range; (b) a probe which is in contact with the front surface of the sample such that the probe faces the focused slow positron beam, the probe (3) being movable along the surface of the sample (2); (c) annihilation gamma-ray detectors; and (d) coincidence annihilation gamma-ray spectrum analyzer connected to the annihilation gamma-ray detectors (5), wherein (e) surface positrons are swarmed in a gap space at the contact point so as to form positronium molecules Ps n (n is an integer equal to or greater than 2), and coherent annihilation gamma-rays generated due to annihilation of the positronium molecules Ps n are detected so as to discriminate the positronium molecules Ps n from positrons and positroniums Ps, thereby measuring on an atomic scale the dynamical properties of the surface layer of the material with a response time shorter than 1 nanosecond. A scanning positronium-molecular microscope according to Claim 3, characterized by further having a function of serving as a scanning probe microscope of a different type such as a scanning tunneling microscope so as to simultaneously perform investigation by scanning of positronium molecules and another investigation by the function of serving as the different type scanning probe microscope.

Inventors: IKEGAMI HIDETSUGU, IKEGAMI, HIDETSUGU
Applicants: JAPAN SCIENCE & TECH CORP, JAPAN SCIENCE AND TECHNOLOGY CORPORATION
Application year: 1997
Main classification: G01N23
IPC codes: G01N23, G21K7, G01Q90