RU2389681C2 - Method for production of nanoelectronic and nanomechanical instruments - Google Patents

Abstract

FIELD: nanotechnologies.

SUBSTANCE: application: in production of nanoelectronics and nanomechanical instruments by method of adsorption - desorption of separate atoms on substrate surface. In method for production of nanoelectronics and nanomechanical instruments by adsorption of separate atoms on surface of substrate and by desorption of separate atoms from substrate surface, instrument is produced by probe arranged perpendicularly to substrate as a combination of nanotubes from oxide bronze alloyed with emission-active atoms of interstitial element, with common formula AxMyOz, where A is symbol of interstitial element selected from elements related to I - III groups of periodical table of chemical elements, M - symbol of bronze-forming oxide element, O - symbol of oxygen, X,Y,Z - stoichiometric coefficients, at the same time atoms adsorbed on surface of substrate arrive from structural channels of probe nanotubes as electric current passes along structural channels due to electric diffusion in structural channels of nanotubes and evaporation from probe with further adsorption on substrate surface, and desorbed atoms from substrate surface arrive into structural channels of probe nanotubes as electric current passes along structural channels, introduction of atoms into structural channels and further electric diffusion of introduced atoms into structural channels of nanotubes.

EFFECT: invention provides for durable operation of probe and improves repeatability of shape in produced elements of nanostructures.

2 cl, 14 dwg, 4 tbl

Description

Usage: in the production of nanoelectronic and nanomechanical devices by adsorption-desorption of individual atoms on the surface of the substrate.

In solid-state technology, two approaches to creating nanostructures are known: top-down and bottom-up. “Top-down” is an approach to cutting nanostructures from source material using lithography (electron, x-ray, using scanning probes). The bottom-up approach uses the method of chemical synthesis and assembly of nanoelements from individual atoms or molecules on a substrate. With the reduction of objects and devices to sizes of the order of hundreds of atoms, the assembly method looks more promising. As stated in the source, "only atoms and molecules can provide high accuracy in dimensional compliance, but it is still not clear how to create a programmable collector." Nanotechnology in semiconductor electronics. / Ans. Editor A.L. Aseev. - Novosibirsk: Publishing House of the SB RAS, 2004. - 368 p.

A known method of molecular beam epitaxy - epitaxial growth in high vacuum. This method allows you to grow heterostructures of a given thickness with monoatomically smooth heteroboundaries. In this case, special substrates suitable for epitaxy are used — they are sufficiently well cleaned of accompanying impurities and with an atomically smooth surface. The flow of atoms to the surface of the substrate is formed in an atomic gun consisting of a Knudsen cell, a diaphragm system, and a resistance heater. Knudsen cells are crucibles made of refractory material (pure boron nitride or graphite). In the case of evaporation of refractory metals, electron-beam heating is used (Z. F. Krasilnik, A. V. Novikov, V. V. Postnikov, D. O. Filatov, A. V. Kruglov. Study of self-organizing Ge islands on Si (100) using an atomic force microscope. Izvestia AN: Physical Series, vol. 63 (2), pp. 287-289 (1999).

The closest known to the described method is the atomic manipulation method. In this method, atomic manipulations to create nanostructures on the surface of a substrate and to obtain images of these nanostructures is performed using the same scanning tunneling microscope. Thus, it becomes possible to inspect the surface, select a place or object of interest to the technologist, carry out the necessary manipulations, and then check the result (see Introduction to Surface Physics / K.Oura, V.G. Lifshits, A.A. Saranin, A.V. .Zotov, M. Katayama. - M .: Nauka, 2006.490 s.).

The main atomic manipulations carried out using a scanning tunneling microscope are the following manipulations:

- lateral movement of the atom along the surface (figure 1, a),

- removal of an atom from the surface (figure 1, b),

- deposition of the atom from the needle onto the surface of the substrate (figure 1, c).

If necessary, to conduct the formation of nanostructures not by monatomic manipulations, but using cluster condensation to create "tubercles" on the surface, the z-pulse method is used (Fig. 2).

However, the known method does not provide the necessary reproducibility of the shape of adsorption nanostructures, is not sufficiently productive, is not subject to automation, and is not sufficiently durable.

The technical problem solved by the described method is the creation of the topology of a nanoelectronic device by the method of molecular beam monoatomic epitaxy.

The specified technical result is achieved by the fact that in the method of manufacturing nanoelectronic devices, an active probe is used, which is a collection of nanotubes doped with emission-active atoms. The emission of atoms of the interstitial elements is excited by the diffusion mechanism during heating and when an electric current is passed along the axis of the nanotubes (electrodiffusion mechanism). The flow of an electric current through the nanotube framework leads to a sharp increase in the diffusion flux due to the effect of entrainment atoms being introduced by the conduction electrons of the nanotube framework.

The invention is illustrated by drawings, where

figure 1 presents a schematic diagram of atomic manipulations using a scanning tunneling microscope: a - moving an atom along the surface of a substrate, b - removing an atom from the surface of the substrate and transferring it to the probe, transferring the atom from the probe to the surface of the substrate;

figure 2. successive stages of the formation of a nanometer-sized tubercle using the z-pulse method are presented, where a - the probe approaches the surface of the substrate, b - the probe contacts the surface of the substrate, c - the probe is retracted, and the "neck" connecting the probe and the surface of the substrate becomes thinner, g - the “neck” is torn, a tubercle from the probe material remains on the surface of the substrate.

figure 3 presents a hypothetical diagram of the formation of tubercles on the surface of the substrate during the evaporation of atoms from the structural channels of the nanotubes of the probe of a scanning tunneling microscope;

figure 4 presents a hypothetical diagram of the formation of depressions on the surface of the substrate during the absorption of atoms of the substrate by the structural channels of the nanotubes of the probe of a scanning tunneling microscope;

while in figure 3 and 4, the following notation is used:

● - position of atoms in the structural channels of nanotubes,

× are the positions of atomic vacancies in the structural channels of nanotubes and in the structure of the substrate,

Ο - position of atoms in the structure of the substrate,

⊗ - position of substrate atoms absorbed by the structural channels of nanotubes,

----- - the line enveloping the surface of the probe or poses,

↓ ↑ - the direction of movement of atoms during the formation of tubercles or depressions;

figure 5 presents the phase diagram of the equilibrium of the quasi-binary section of the alloy system V ₂ O ₅ - Na _x ;

figure 6 presents the spatial crystal structure of Na _0.33 V ₂ O ₅ (β-phase);

Fig. 7 shows an electric circuit for measuring the change in weight during evaporation of a sample in an electric field with a maximum intensity of E = 40 V / cm, with an additional ion-optical system to a mass spectrometer, including a pulling electrode 1 in the form of a hollow cone and a compression lens 2 in the form of a hollow cylinder;

on Fig presents frames before (left - 8A) and after (right - 8b) the emission of atoms from an oxide bronze crystal;

figure 9 presents the morphology of the tubercles after the emission of sodium atoms from a crystal of oxide bronze;

figure 10 shows an example of the growth of an individual gold nanograin after emission and adsorption of sodium atoms in the center of the original frame with the parameters of atomic emission and scanning, similar to the mode of Fig. 8. The sizes of the frames before the emission (left) and after the emission (right) are also 200 × 200 nm, the maximum height spread in both frames is about 40 nm;

Fig. 11 shows an example of the appearance of a columnar nanostructure on the surface of a gold film after emission in the uniform scanning mode of the entire field of the initial frame for 100 s with atomic emission and scanning parameters similar to the mode of Fig. 8. The size of these frames is 1000 × 1000 nm, the spread in heights in both frames is about 180 nm;

on Fig shows the process of formation of the pits during the desorption of gold atoms of the substrate into a single crystal of sodium bronze oxide with the decay of nanograins larger than 100 × 100 nm into smaller grains after a single desorption by a similar pulse of Fig.8;

13 shows the decay of a nanograin upon desorption of a part thereof into an oxide bronze crystal;

on Fig shows the process of removing nanograins by desorption from the surface and transferring them to the nanotubes of a single crystal of bronze oxide (nanoheter).

The application of various structural elements of nanoelectronic devices to the substrate by the method of monatomic adsorption and, at the same time, the control of the results of the technological process is carried out by tunnel microscopy.

In the bipolar pulse mode of a tunneling microscope, the emitter sequentially performs three probe functions: an emitter of interstitial atoms (with a negative polarity on the probe relative to the substrate) to create a topological pattern on the substrate and a traditional scanning probe (with positive polarity on the probe relative to the substrate) to obtain an image of atomic condensation results . It is assumed that the positive polarity on the probe relative to the substrate is "blocking" for atomic emission.

Thus, thermal and electrical excitation in the structural channels of nanotubes creates a directed flow of single atoms controlled by a given program to the surface of the substrate. If the emitter is made in the form of a point with longitudinally oriented structural channels and the flat substrate is arranged perpendicular to the structural channels, then atomic emission from the structural channels will lead to controlled atomic condensation on the substrate.

In addition, when using relatively long pulses, it is possible to smoothly switch from monatomic condensation from the monatomic flow regime to the monatomic avalanche mode for the production of nanosized elements (tubercles) by the method of cluster condensation.

Thus, by varying the chemical composition, temperature, current, and pulse duration of the probe, as well as the temperature and type of substrate, it is possible to obtain metallic nanosized layers and synthesize solid solutions and chemical compounds. When choosing an intermediate medium between the probe and the substrate (atmosphere, vacuum, inert or chemically active gas, liquid), it is possible to carry out redox reactions on the resulting condensate and to carry out other programmable nanometallurgical processes.

When describing the physical model of atomic condensation technology, it is methodologically convenient to first consider the physical model of atomic diffusion electron transfer in the structural channels of the probe material, and then the structure of the condensate obtained on the substrate surface.

According to preliminary experimental data, a probe material with emission-active atoms of interstitial elements can be a single crystal of any oxide bronze with the general formula A _X M _Y O _Z , where A is the symbol of the interstitial element, M is the symbol of the element of bronze-forming oxide, O is the oxygen symbol , X, Y, Z - stoichiometric coefficients. Under the elements of implementation refers to the elements of I, II and III groups of the Periodic system.

The main measurements were carried out on single crystals of sodium vanadium oxide bronze Na _0.33 V ₂ O ₅ (β-phase) because this bronze was most studied according to publications in Russia and abroad. Almost all thermally decomposing salts with sodium cations are used to synthesize sodium vanadium oxide bronze Na _0.33 V ₂ O ₅ (β-phases).

In the solid-phase method for producing oxide bronze, sodium atoms penetrate the crystal lattice of vanadium oxide due to internal diffusion processes. Stoichiometric mixtures of the corresponding substances are heated in an atmosphere of air to a temperature of 400 ° C-600 ° C and periodically triturated. The process is carried out in a bulk charge, which facilitates the release of gaseous products and contributes to the fastest passage of the reaction, which has the form (one of the options): 0.33 NaCl + V ₂ O ₅ = Na _0,33 V ₂ O ₅ + 0,165 Cl ₂ . Also, as sodium-containing compounds, you can use: NaOH, NaNO ₃ , Na ₂ SO ₄ , Na ₂ CO ₃ . The phase diagram of the equilibrium of the quasi-binary section of the system of alloys V ₂ O ₅ - Na _x is presented in figure 5.

β-phase is a chemical compound of variable composition, Fig.1.

The density of the stoichiometric composition of the β phase and its components is presented in Table 1.

Table 1. The density of bronze and its components Substance ρ, gcm ^-3 Na _0.33 V ₂ O ₅ 3.57 Na 0.14 V 1.92 O 1.51

The structure of sodium vanadium bronze oxide (β phase) belongs to the monoclinic syngony with the C2 / m space group. The unit cell contains six formula units. The lattice parameters are given in table 2.

Table 2. Crystallochemical parameters of the structure of Na _0.33 V ₂ O ₅ (β-phase) a · 10 ^-10 , m b · 10 ^-10 , m s · 10 ^-10 , m β, hail 10,078 3,612 15,435 109.6

The spatial structure of Na _0.33 V ₂ O ₅ (β-phase) is shown in Fig.2. The vanadium atoms V ₁ and V ₂ are located inside the deformed oxygen octahedra. The double chains thus formed parallel to the b axis are interconnected by a common oxygen atom. The third atom of vanadium V ₃ is located inside a bipyramid with a triangular base, at the tops of which there is oxygen. These bipyramids also form a chain along the b axis. Thus, the so-called tunnels are formed, surrounded by vanadium - the oxygen skeleton. Inside such tunnels, interstitial metal ions (sodium ions) occupying symmetrical positions are located. Spatial crystal structure

Na _0.33 V ₂ O ₅ (β-phase) is shown in Fig.6.

Thus, as follows from table 2. and figure 2, the distance between the sodium atoms along the length of the structural channels is 3,612 · 10 ^-10 m

Na _0.33 V ₂ O ₅ (β-phase) at low temperatures (up to 650 K) is an n-type semiconductor. In accordance with the proposed energy scheme, the conductivity of a single crystal at room temperature is carried out mainly by electrons entering the conduction band from donor levels, which are formed as a result of the introduction of sodium atoms into the octahedral voids V ₂ O ₅ . It should be noted that the values of electrical resistivity along the b axis and perpendicular to it are equal respectively: ρ_ = 4.6 · 10 ^-2 Ohm · cm; ρ _⊥ = 29 Ohm · cm. Large anisotropy of electrical resistance and predominant conductivity parallel to the tunnel axis b.

In the temperature range 650–970 K, the appearance of a metallic type of conductivity along the b direction is observed in the temperature dependence of electrical conductivity, while the activation energy decreases to zero.

Sodium atoms (“element - guest”) have relatively low binding energy in the structural channels of vanadium — the oxygen skeleton (“lattice - host”); therefore, they have sufficiently high thermal and electrical diffusion mobility along the length of the channels.

When a β-phase single crystal is heated in the absence of an external force field, in accordance with the first Fick law, the diffusion flux density J, g · cm ² · s ^-1 , of sodium atoms in the structural channels is proportional to the diffusion coefficient D and the concentration gradient C:

The diffusion coefficient D, cm ² · s ^-1 , is defined as the product of the linear velocity under thermal influence ν _T , cm · s ^-1 , by the length of the diffusion jump l, cm:

For the diffusion of sodium atoms in the structural channels of the vanadium - oxygen skeleton, the linear thermal velocity is determined as the quotient of the division of the diffusion flux density J by the density of sodium atoms in bronze ρ, g · cm ^-3 :

In accordance with table 1 ρ = 0.14 g · cm ^-3 .

The length of the diffusion jump l is defined as the distance between the two equilibrium positions of the diffusing sodium atom in the structural channel of the vanadium – oxygen skeleton. In accordance with Table 2, l = 3.612 · 10 ^-10 m. For known values of ν _T and l, one can determine the duration of the diffusion jump τ, s, and the frequency of release of sodium atoms from the emission surface f, s ^-1 .

Thus, in order to determine the diffusion coefficient of sodium in structural channels, it is necessary to experimentally determine the density of the sodium vaporization flux from the β-phase sample.

Due to the fact that sodium atoms are in the structural channels in the ionized state of Na ⁺ , the numerical value of the diffusion coefficient characterizes not only the result of heat exposure, but also the effect of entrainment of the conduction electrons of vanadium - oxygen skeleton by diffusing sodium ions. When a coupled ion-electron pair reaches the “solid” - “gas (vacuum)” interface, low-temperature quasi-neutral plasma is emitted.

The effective charge of sodium ion Na ⁺ is determined by the ratio:

- ток положительных ионов натрия Na⁺ в структурных каналах при термическом возбуждении в нулевом внешнем электрическом поле,

- ток электронов ванадий - кислородного каркаса, возникающий за счет эффекта увлечения электронов положительными ионами натрия Na⁺ при термическом возбуждении. Если предположить, что ток ионов равен току электронов, то в соответствии с формулой (4) эффективный заряд положительного иона натрия Na⁺ будет равен нулю, Z₀=0.Where

- the current of positive sodium ions Na ⁺ in the structural channels during thermal excitation in zero external electric field,

- current of electrons of vanadium - oxygen skeleton, arising due to the effect of electron entrainment by positive sodium ions Na ⁺ during thermal excitation. If we assume that the ion current is equal to the electron current, then, in accordance with formula (4), the effective charge of the positive sodium ion Na ⁺ will be zero, Z ₀ = 0.

When a β-phase single crystal is heated in an external electric field, the product С · ν _{E is} added to the equation of the first Fick law (1), where ν _E is the average additional velocity of the sodium atom in the Na ⁺ state in the electric field:

Under the influence of an external electric field, the electron current will significantly exceed the current of sodium ions Na ⁺ , and the value of the effective charge Z ₀ will characterize the number of conduction electrons that “carry away” one positive sodium ion, minus one. So, for example, if the effective charge of a positive sodium ion is Z ₀ = -10, then this means that 11 conduction electrons form a negative dynamic charge. When you turn off the external electric field, the negative dynamic charge disappears.

It should be noted that a negative effective charge characterizes an increase in the diffusion flux of sodium atoms in the Na ⁺ state during the flow of electrons along structural channels due to an increase in the frequency of jumps from one equilibrium position to another with a constant diffusion jump length l.

The effective charge of a positive sodium ion Na ⁺ is determined by a formula similar to (4):

и

ионный и электронный ток при диффузии во внешнем электрическом поле.Where

and

ion and electron current during diffusion in an external electric field.

Thus, when heated in the absence of an external electric field, sodium atoms in the structural channels diffuse in the Na ⁺ state with a zero effective charge, and when an external electric field is applied, they acquire a negative effective dynamic charge, which contributes to an increase in the density of the flux of sodium atoms on the “solid” interface - "gas (vacuum)."

To measure the fluxes of evaporation of sodium atoms, a β-phase single crystal obtained by the Bridgman method was used. The initial charge was synthesized by carbonate technology. The sample was in the form of a cylinder with a diameter of 5 mm and a length of 10 mm.

The measurements were carried out on a universal thermogravimetric installation with exposure to the sample under study electric and magnetic fields. The setup is equipped with a quadrupole mass spectrometer for analyzing the gas phase above the surface of the sample. The installation diagram is shown in Fig. 7, which shows the electrical circuit for measuring the change in weight during evaporation of the sample in an electric field with a maximum intensity of E = 40 V / cm, with an additional ion-optical system to the mass spectrometer, including a pulling electrode 1 in the form of a hollow a cone and a compression lens 2 in the form of a hollow cylinder. The measurement results are presented in tables 3 and 4.

Table 3. Parameters of diffusion fluxes of sodium atoms upon heating a sample of a single crystal of the β phase in vacuum at zero external electric field t, ° C

г·см^-2·с^-1

g · cm ^-2 · s ^-1

cm ^-2 · s ^-1

A cm ^-2

A cm ^-2 ν _T
cm · s ¹ Z ₀ D
cm ² s ^-1 f
c ^-1 580 2.6 · 10 ^-11 6.810 ¹¹ 1.1 · 10 ^-6 1.1 · 10 ^-6 1.9 · 10 ^-10 0 6.7 · 10 ^-18 5.2 · 10 ^-3 700 7.6 · 10 ^-8 2 · 10 ¹⁵ 3.2 · 10 ^-4 3.2 · 10 ^-4 5.5 · 10 ^-7 0 2 · 10 ^-14 fifteen

Table 4. Parameters of diffusion fluxes of sodium atoms upon heating a sample of a β-phase single crystal in vacuum in an external electric field t, ° C

г·см^-2·с^-1

g · cm ^-2 · s ^-1

cm ^-2 · s ^-1

A cm ^-2

A cm ^-2 ν _E
cm s ^-1 Z ₀ D
cm ² s ^-1 f
c ^-1 580 4.6 · 10 ^-8 1.2 · 10 ¹⁵ 1.9 · 10 ^-4 1 · 10 ^-1 3.3 · 10 ^-7 -520 1.7 · 10 ^-15 9 700 5.4 · 10 ^-7 1.410 ¹⁷ 2.2 · 10 ^-2 1.4 · 10 ^-1 3.8 · 10 ^-5 -5 1.9 · 10 ^-13 1 · 10 ³

The first experiments on the direct observation of adsorption-desorption processes on a substrate using an emission-active probe were carried out using a scanning probe microscope in a tunnel mode.

Adsorption-desorption processes on the substrate were carried out in a natural atmosphere of air without evacuation. Under these conditions, an adsorbate with a thickness of 20-30 Angstrom from a water film with natural atmospheric impurities characteristic of all solid surfaces is constantly located on the surface of the substrate. Sodium atoms adsorbed on the surface of the substrate were formed in the form of tubercles containing up to hundreds of atoms and, apparently, agglomerates of sodium salts, which are actively formed during the interaction of sodium with an adsorbed film of water.

A scanning tunneling microscope was used to study adsorption-desorption processes because it combines the two functions necessary for experiments with the emission of atoms from a single crystal of oxide bronze. It has a record for microscopy resolution of surface structures, up to atomic in the absence of adsorbates, and during its operation, scanning, moves its probe needle along the surface at an adjustable distance from it with the possibility of this needle hanging above certain points on the surface.

A universal probe needle was made from a single crystal of oxide bronze, with the help of which a frame was obtained on the same portion of the substrate by scanning the relief with a tunnel current, the point at which the probe was brought in, the emission of sodium atoms was performed, and then the initial frame was re-scanned for registration changes in the relief of the substrate after emission.

Tunnel current scanning was carried out at small positive voltages from 0 to + 1 V on the probe, atomic emission was carried out at negative voltages up to -5 V. The substrate in the scanning and atomic emission modes had zero potential. Both during scanning and during atomic emission, the microscope automatically maintained the total specified electric current at a level set by the operator from 0.1 to 16 nA. During scanning, the specified current was electronic, and during atomic emission it is equal to the difference between the emission current of positive ions and the current of tunneling electrons.

The preparation of the probes was carried out by splitting the single crystal. In this case, needles were obtained, from which the sharpest ones with a radius of curvature of about 4-10 nm were chosen for work. To fix a fragile needle-shaped single crystal in a microscope, it was first soldered with its rear end into a thin-walled stainless steel tube with an external diameter of 0.8 mm. The sharp end of the needle protruded 1-2 mm from the tube. Then the tube was clamped in the needle holder of the microscope.

As a substrate, a copper substrate with a sprayed film of pure (99.98 wt.%) Gold of 20 μm thick was chosen, which was both chemically inert and ideally worked without noise in the scanning mode by tunneling current. The gold surface had a pronounced polycrystallinity with a grain size of about 1 μm. To observe the processes of atomic emission, a survey frame of about 10 × 10 μm in size was first made, on which an acceptable place was chosen, for example, a flat grain surface. Frames with pronounced emission results had a size of not more than 1 × 1 μm, but the tubercles themselves, which are the result of atomic emission, were observed only with even greater magnification and even smaller frame size, respectively, starting from frames with a size of 200 × 200 nm. Further reduction of the frame to sizes less than 100 × 100 nm in order to further examine the emitted tubercles in more detail did not give results due to the physical limitation of the resolution of the adsorbate.

The result of experiments with the operation of oxide bronze crystals in a tunneling microscope was not only the expected observation of the emission of atoms from them with adsorption on the surface of the substrate, but also several additional phenomena. The processes of structural rearrangement of the surface adsorbing these emitted atoms were discovered, and, in addition, the desorption of sodium atoms from the gold surface by their pulling (gettering) into a single oxide bronze crystal by the field evaporation mechanism in an opposite electric field was discovered.

On Fig. A characteristic result is shown for the main observed process of emission of sodium atoms from the structural channels of nanotubes of a single crystal probe from sodium vanadium oxide bronze to the substrate surface. Both frames, 8a) - left and 8b) - right, were obtained by scanning at a tunneling current of 5 nA with a scanning voltage of +0.5 V on the probe. The frame sizes are 100 × 100 nm, the maximum spread in heights is 9 nm in the left frame and 10 nm in the right frame.

On the left frame (figa) shows the original surface of the gold substrate. To carry out the adsorption of sodium atoms on a gold substrate, the probe was placed in the center of the left frame area. The gap was about 1 nm between its end and the substrate. At the same time, a negative voltage of -5 V was applied to the probe for the emission of sodium atoms, maintaining a total tunneling and emission current of 5 nA for 5 s. Then a scan was carried out and the right frame was obtained (Fig. 8b).

The diameter of the probe tip located in the immediate vicinity of the substrate was only 4–10 nm, and the diameter of the spot of emission of sodium atoms — the region of origin of the tubercles — was about 80–100 nm. Thus, the emission of sodium atoms occurs from many channels located at a distance of about 50 nm from the substrate, where the field strength drops to 1 MV / cm, when the voltage reaches 50 MV / cm at the tip of the probe.

The morphology of the tubercles after the emission of sodium atoms from an oxide bronze crystal is shown in Fig. 9. The morphology of the tubercles in the frame after the emission of sodium atoms (Fig. 9) was evaluated using cross sections taken along this frame, as well as particle size analysis. The diameter of the formed tubercles is from 0.5 nm to 30 nm, and the diameter distribution is rather uniform. The distance between the centers of the tubercles is from 1 to 20 nm. The height of the tubercles, measured by sections, is from 0.5 to 5 nm. In addition to the appearance of tubercles, processes of structural rearrangement of the surface of a gold substrate are quite often observed, on which sodium atoms emitted from a single crystal of oxide bronze are adsorbed.

Figure 10 shows an example of the growth of an individual gold nanograin after emission and adsorption of sodium atoms in the center of the original frame with the parameters of atomic emission and scanning, similar to the mode of Fig. 8. The sizes of the frames before emission, shown in Fig. 10a (left), and after the emission, presented in Fig. 10b (right), are also 200 × 200 nm, the maximum height spread in both frames is about 40 nm.

Figure 11 shows an example of the appearance of a columnar nanostructure on the surface of a gold film after emission in the uniform scanning mode of the entire field of the initial frame for 100 s with atomic emission and scanning parameters similar to the regime in Fig. 8. The size of these frames is 1000 × 1000 nm, the spread in heights in both frames is about 180 nm.

The processes of desorption of gold surface atoms by the field desorption mechanism with their introduction into the structural channels of oxide bronze nanotubes were observed at the same voltage for some time, but with positive polarities of this voltage on the probe.

12 shows how, after applying +5 V for 5 s with a current of 5 nA, when the probe is applied 1 nm from the substrate to the point marked in the initial frame by the circle, a small depression, shown in the second frame, first appears. In subsequent similar cycles of voltage application, this recess develops as a result into the fossa shown in the fourth frame with a size of about 20 nm in diameter and 15 nm in depth. The size of all frames is 200 × 200 nm; the maximum spread in heights is about 40 nm. It should be noted that the observed field desorption is fundamentally different from adsorption of sodium atoms - the desorption locality is much higher and slightly larger than the probe tip diameter, when the diameter of the adsorption spot is much larger, about 100 nm.

Structural rearrangement of the surface is also observed during atom desorption. On Fig shows the case of the decay of nanograins larger than 100 × 100 nm into smaller grains after a single desorption similar to Fig.8 pulse. The size of the formed pit here is also not large, about 30 Angstroms. The frame size in Fig.9 - 200 × 200 nm, the maximum spread of heights - about 80 nm.

The desorption result is also interesting when a +5 V voltage is applied to the probe and uniformly scans the entire frame for 20 s at a distance of 1 nm of the probe from the surface. The oxide bronze single crystal probe serves as a “nano getter” here, drawing in all the gold nanopowders weakly attached to the substrate. After the operation of this “nano getter”, the surface of the gold film (Fig. 10, frame on the left), on which there are many nanograins with a diameter of 2-10 nm, began to have a pronounced porous character with pores with a diameter of 2-10 nm and a depth of 2-10 nm. The frame size in FIG. 10 is 200 × 200 nm, the maximum height spread is about 20 nm in the original frame and about 30 nm in the frame with pores.

Thus, the use of the described method for the production of nanoelectronic devices makes it possible to carry out adsorption processes in the mode of transfer of monatomic particles or atomic packets of atoms of elements of groups I, II, and III of the Periodic system from the structural channels of oxide bronze nanotubes onto the surface of substrates and also carry out desorption processes of transfer of surface atoms or atomic packages of elements of groups I, II, and III of the Periodic system from the surface of the substrates to the structural channels of oxide nanotubes of oxide bronzes with n their accumulation in the probe volume (gettering effect) with simultaneous visualization of the results on the substrate surface in the mode of the probe electron microscope by manual or automatic control.

Thus, the technical result obtained by the implementation of the described invention is expressed in increasing the durability of the probe and in improving the reproducibility of the shape of the obtained elements of nanostructures.

In addition, it is possible to carry out adsorption of atoms on a substrate and desorption of atoms from a substrate for a long time without changing the shape of the probe and use automatic control of adsorption-desorption processes in a wide range of flux density of adsorbed and desorbed atoms.

Sources of information for patent applications

1. Z.F. Krasilnik, A.V. Novikov, V.V. Postnikov, D.O. Filatov, A.V. Kruglov. Investigation of self-organizing Ge islands on Si (100) using an atomic force microscope. "Proceedings of the Academy of Sciences: Physical Series", t. 63 (2), pp. 287-289 (1999).

2. Introduction to surface physics / K. Oura, V. G. Lifshits, A. A. Saranin, A. V. Zotov, M. Katayama. - M .: Nauka, 2006.490 s.

3. Fotiev A.A., Volkov V.L., Kapustkin V.K. Vanadium oxide bronzes. M .: Nauka, 1978.- 176 p.

4. Ozerov R.P. Crystal chemistry of oxygen vanadium bronzes. M.: Crystallography, 1957, v. 2, issue 2, pp. 226-232.

5. Ornatskaya Z.I. Electrical properties of oxygen vanadium bronzes. FTT, 1964, v.6. issue 4, p. 1254-1256.

6. Fotiev A.A., Ivakin A.A. Vanadium compounds of alkali metals. Sverdlovsk: UV USSR Academy of Sciences, 1970, p. 153.

7. Fotiev A.A., Volkov V.L., Kapustkin V.K. Semiconductor - metal phase transition in oxygen vanadium bronzes. DAN USSR, 1975, t.223, No. 6, pp. 1398-1400.

8. Petrov BC, Fonarev G.S., Kozhevnikov V.L. Construction of a phase T-δ equilibrium diagram of YBa ₂ Cu ₃ O _7-δ from the data on the rate of transformation during dissociation in vacuum. Superconductivity: physics, chemistry, technology, vol. 5, No. 6. 1992, p. 1090-1096.

9. Petrov BC A complex of measuring modules for determining the thermodynamic and kinetic constants of processes occurring in cathode, getter, superconducting, radar absorbing and sensor materials when heated in vacuum and under the influence of electric and magnetic fields. Perspective Technologies, Materials and Equipments of Solid-State Electronic Components: Proceedings of 2 ^nd Russian-Japanese Seminar. - M .: 2004, MISA Publishing, pp.138-143.

10. Velichko A.A., Parchment A.L., Stefanovich GB, Putrolayn V.V., Cheremisin A.B., Manuylov S.A., Kuldin N.A., Loginov B.A. Obtaining nanostructures based on transition metal oxides. Nanotechnology. No. 2. S.89-95 (2006).

11. V.M. Kornilov, A.N. Lachinov, B.A. Loginov. Features of the formation of nanostructures in the STM study of the silicon surface. Surface. X-ray, synchrotron and neutron studies, 2006, 5, pp. 11-14.

Claims (2)

1. A method of manufacturing nanoelectronic and nanomechanical devices by adsorption of individual atoms on the surface of the substrate and by desorption of individual atoms from the surface of the substrate to form a nanoelectronic or nanomechanical device with visualization of the results of the process at all stages, characterized in that the formation of the device is carried out by a probe placed perpendicular to the substrate and made in the form of a combination of oxide bronze nanotubes doped with emission-active atoms of the interstitial element, with a total by the formula A _X M _Y O _Z , where A is the symbol of the insertion element selected from elements belonging to groups I to III of the Periodic table of chemical elements, M is the symbol of the element of bronze-forming oxide, O is the symbol of oxygen, X, Y, Z are stoichiometric the coefficients adsorbed on the surface of the substrate, the atoms come from the structural channels of the nanotubes of the probe by passing an electric current along the structural channels due to electrodiffusion in the structural channels of the nanotubes and evaporation from the probe, followed by adsorption on the surface under ozhki and desorbing atoms from the surface of the substrate enter the structural channels probe nanotubes by passing an electric current along the channel due to structural oriented in the direction of the structural channels field evaporation from the substrate surface, the introduction of atoms in the structural channels and further electrodiffusion interstitial atoms in the structural channels nanotubes. 2. The production method of nanoelectronic and nanomechanical devices according to claim 1, characterized in that the formation of the device is carried out by a probe with a radius of curvature of the tip of about 4-10 nm.

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