JP4791948B2 - Information recording / reproducing device - Google Patents

Description

  The present invention relates to an information recording / reproducing apparatus having a high recording density.

  In recent years, small portable devices have spread worldwide, and at the same time, with the rapid progress of high-speed data transmission networks, the demand for small, large-capacity nonvolatile memories has been rapidly expanding. Among them, the NAND flash memory and the small hard disk drive (HDD) have achieved a rapid development of the recording density and have formed a large market.

  Under such circumstances, several ideas for a new memory aiming to greatly exceed the recording density limit have been proposed.

  For example, a PRAM (phase change memory) uses a material that can take two states of an amorphous state (off) and a crystalline state (on) as a recording material, and the binary data “0”. , “1” is used to record data.

  For writing / erasing, for example, an amorphous state is created by applying a high power pulse to the recording material, and a crystalline state is created by applying a small power pulse to the recording material.

Reading is performed by passing a small read current that does not cause writing / erasing to the recording material and measuring the electrical resistance of the recording material. The resistance value of the recording material in the amorphous state is larger than the resistance value of the recording material in the crystalline state, and the difference is about 10 ³ .

  The biggest feature of PRAM is that it can operate even when the element size is reduced to about 10 nm. In this case, a recording density of about 10 Tbpsi (tera bite par square inch) can be realized. One of the candidates for the conversion (see, for example, Patent Document 1).

  In addition, a new memory having an operation principle very different from that of PRAM has been reported (for example, see Patent Document 2).

  According to this report, a typical example of a recording material for recording data is nickel oxide, and similarly to the PRAM, a high power pulse and a low power pulse are used for writing / erasing. In this case, it has been reported that the power consumption at the time of writing / erasing is smaller than that of the PRAM.

  Up to now, the operation mechanism of this new memory has not been elucidated, but reproducibility has been confirmed and it is considered as another candidate for increasing the recording density. In addition, several groups have tried to elucidate the operating mechanism.

  In addition to these, a MEMS memory using MEMS (micro electro mechanical systems) technology has been proposed (see, for example, Non-Patent Document 1).

  In particular, a MEMS memory called Millipede has a structure in which a plurality of cantilevers arranged in an array and a recording medium coated with an organic substance face each other, and the probe at the tip of the cantilever is applied to the recording medium with an appropriate pressure. In contact.

  The writing is selectively performed by controlling the temperature of the heater added to the probe. That is, when the temperature of the heater is increased, the recording medium is softened, and the probe is recessed into the recording medium, thereby forming a recess in the recording medium.

  Reading is performed by scanning the probe with respect to the surface of the recording medium while supplying a current that does not soften the recording medium to the probe. When the probe falls into the depression of the recording medium, the temperature of the probe decreases and the resistance value of the heater increases. Therefore, data can be sensed by reading the change in resistance value.

  The greatest feature of a MEMS memory such as millipede is that it is not necessary to provide a wiring in each recording section for recording bit data, and therefore the recording density can be dramatically improved. At present, a recording density of about 1 Tbpsi has already been achieved (for example, see Non-Patent Document 2).

  Also, following the announcement of Millipede, recently, attempts have been made to achieve significant improvements in terms of power consumption, recording density, operating speed, etc. by combining MEMS technology with a new recording principle.

  For example, there has been proposed a method of recording data by providing a ferroelectric layer on a recording medium and applying a voltage to the recording medium to cause dielectric polarization in the ferroelectric layer. According to this method, there is a theoretical prediction that the interval (recording minimum unit) between the recording units that record bit data can be brought close to the unit cell level of the crystal.

  If the minimum recording unit is one unit cell of the ferroelectric layer crystal, the recording density becomes a huge value of about 4 Pbpsi (pico bite par square inch).

Recently , due to the proposal of a readout method using SNDM (Scanning Nonlinear Dielectric Microscope) , this new memory has made considerable progress toward practical use (for example, see Non-Patent Document 3).

  In the example of the present invention, a nonvolatile information recording / reproducing apparatus with high recording density and low power consumption is proposed.

An information recording / reproducing apparatus according to an example of the present invention includes a recording layer and means for recording data by applying a voltage to the recording layer to cause a resistance change in the recording layer, and the recording layer is i. AxM1yX1z A layer made of the first compound (where A and M1 are cationic elements, X1 is at least one element selected from O, S, Se, N, Cl, Br, and I, 0.1 ≦ x ≦ 2.2, 0.5 ≦ y ≦ 2.5, is 1.5 ≦ z ≦ 4.5.), and, ii. at least one transition element, and made of a second compound having a vacant site that can accommodate the cation element Includes a structure in which layers are stacked .

  According to the example of the present invention, a non-volatile information recording / reproducing apparatus with high recording density and low power consumption can be realized.

  The best mode for carrying out an example of the present invention will be described below in detail with reference to the drawings.

1. Overview
(1) In the information recording / reproducing apparatus according to the first example of the present invention, the recording layer is composed of a composite compound having at least two kinds of cation elements. Further, at least one kind of cation element is a transition element having d orbital incompletely filled with electrons, and the shortest distance between adjacent cation elements is 0.32 nm or less.

  Specifically, the recording layer is composed of the following materials.

· Chemical formula 1: A _x M _{y X 4}
A is Na, K, Rb, Be, Mg, Ca, Sr, Ba, Al, Ga, Mn, Fe, Co, Ni, Cu, Zn, Si, P, S, Se, Ge, Ag, Au, Cd , Sn, Sb, Pt, Pd, Hg, Tl, Pb, Bi.

  A is preferably at least one element selected from the group consisting of Mg, Al, Mn, Fe, Co, Ni, Zn, Cd, and Hg. This is because, when these elements are used, the ionic radius for maintaining the crystal structure is optimal, and the ion mobility can be sufficiently secured.

  Furthermore, A is more preferably at least one element selected from Zn, Cd, and Hg. This is because, when these elements are used, position inversion between cations is less likely to occur, and switching can be stably repeated.

  M is at least one selected from the group consisting of Al, Ga, Ti, Ge, Sn, V, Cr, Mn, Fe, Co, Ni, Nb, Ta, Mo, W, Tc, Re, Ru, and Rh. It is an element.

  M is preferably at least one element selected from the group consisting of V, Cr, Mo, W, Mn, Tc, Re, Fe, Co, Ni, Al, and Ga. This is because the use of these elements makes it easier to control the electronic state in the crystal.

  Furthermore, M is preferably at least one transition element selected from the group 1 consisting of Cr, Mo, W, Mn, Tc, and Re. This is because when these elements are used, the matrix structure is stably maintained, so that switching can be stably repeated.

  Further, it is preferable that M contains at least one element selected from the group of Fe, Co, Ni, Al, and Ga in addition to the group 1 transition element. This is because if these elements are used in place of some of the elements of group 1, the matrix structure is maintained more stably, and switching can be repeated more stably.

  A and M are different elements, and at least one of them is a transition element having a d orbital in which electrons are incompletely filled. X is at least one element selected from the group of O and N. The molar ratios x and y shall satisfy 0.1 ≦ x ≦ 2.2 and 1.5 ≦ y ≦ 2, respectively.

· Chemical formula 2: A _x M _{y X 3}
A is Na, K, Rb, Be, Mg, Ca, Sr, Ba, Al, Ga, Mn, Fe, Co, Ni, Cu, Zn, Si, P, S, Se, Ge, Ag, Au, Cd , Sn, Sb, Pt, Pd, Hg, Tl, Pb, Bi.

  A is preferably at least one element selected from the group consisting of Mg, Al, Mn, Fe, Co, Ni, and Zn. This is because, when these elements are used, the ionic radius for maintaining the crystal structure is optimal, and the ion mobility can be sufficiently secured.

  M is at least one selected from the group consisting of Al, Ga, Ti, Ge, Sn, V, Cr, Mn, Fe, Co, Ni, Nb, Ta, Mo, W, Tc, Re, Ru, and Rh. It is an element.

  M is preferably at least one element selected from the group consisting of V, Cr, Mn, Fe, Co, and Ni. This is because the use of these elements makes it easier to control the electronic state in the crystal.

  A and M are different elements, and at least one of them is a transition element having a d orbital in which electrons are incompletely filled. X is at least one element selected from the group of O and N. The molar ratios x and y shall satisfy 0.5 ≦ x ≦ 1.1 and 0.9 ≦ y ≦ 1, respectively.

· Chemical formula 3: A _x M _{y X 4}
A is Na, K, Rb, Be, Mg, Ca, Sr, Ba, Al, Ga, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Si, P, S, Se, Ge , Ag, Au, Cd, Sn, Sb, Pt, Pd, Hg, Tl, Pb, Bi.

  A is preferably at least one element selected from the group consisting of Mg, Al, Ga, Sb, Ti, Mn, Fe, and Co. This is because, when these elements are used, the ionic radius for maintaining the crystal structure is optimal, and the ion mobility can be sufficiently secured.

  M is at least one element selected from the group consisting of Al, Ga, Ti, Ge, Sn, V, Nb, Ta, Cr, Mn, Mo, W, Ir, and Os.

  M is preferably at least one element selected from the group consisting of Cr, Mn, Mo, and W. This is because the use of these elements makes it easier to control the electronic state in the crystal.

  A and M are different elements, and at least one of them is a transition element having a d orbital in which electrons are incompletely filled. X is at least one element selected from the group of O and N. The molar ratios x and y shall satisfy 0.5 ≦ x ≦ 1.1 and 0.9 ≦ y ≦ 1, respectively.

The above three materials _{(A x M y X 4,} A x M y X 3, A x M y X 4) molar ratio x, relates to y, the lower limit of the numerical range, set to maintain the crystal structure The upper limit is set to control the electronic state in the crystal.

  The recording layer employs one of the following crystal structures.

・ Spinel structure
・ Cryptomerene structure
・ Ilmenite structure
・ Malokite structure
・ Hollandite structure
・ Heterolite structure
・ Rams delight structure
・ Delafossite structure
・ Olivine structure
Α-NaFeO ₂ structure
-LiMoN ₂ structure By adopting these crystal structures, the shortest distance between adjacent cation elements is 0.32 nm or less, and the electron conductivity of the recording layer can be improved.

  By using the recording layer as described above, with respect to the recording density, in principle, the Pbpsi class can be realized, and furthermore, low power consumption can be achieved.

  (2) In the information recording / reproducing apparatus according to the second example of the present invention, the recording layer is a first compound represented by i. AxM1yX1z (where A and M1 are cationic elements, and X1 is O, S, At least one element selected from Se, N, Cl, Br, I, 0.1 ≦ x ≦ 2.2, 0.5 ≦ y ≦ 2.5, 1.5 ≦ z ≦ 4.5), and ii. At least one transition element And a second compound having void sites that can accommodate the cation element of the first compound.

The second compound is
Chemical formula 4: xM2X2 ₂
Where □ is a void site containing a cationic element, M2 is from Ti, Ge, Sn, V, Cr, Mn, Fe, Co, Ni, Nb, Ta, Mo, W, Re, Ru, Rh At least one element selected, X2, is at least one element selected from O, S, Se, N, Cl, Br, and I, 0.3 ≦ x ≦ 1.

Chemical formula 5: □ xM2X2 ₃
Where □ is a void site containing a cationic element, M2 is from Ti, Ge, Sn, V, Cr, Mn, Fe, Co, Ni, Nb, Ta, Mo, W, Re, Ru, Rh At least one element selected, X2, is at least one element selected from O, S, Se, N, Cl, Br, and I, 1 ≦ x ≦ 2.

Chemical formula 6: □ xM2X3 ₄
Where □ is a void site containing a cationic element, M2 is from Ti, Ge, Sn, V, Cr, Mn, Fe, Co, Ni, Nb, Ta, Mo, W, Re, Ru, Rh At least one element selected, X3, is at least one element selected from O, S, Se, N, Cl, Br, and I, 1 ≦ x ≦ 2.

Chemical formula 7: xM2POz
Where □ is a void site containing a cationic element, M2 is from Ti, Ge, Sn, V, Cr, Mn, Fe, Co, Ni, Nb, Ta, Mo, W, Re, Ru, Rh At least one element selected, P is a phosphorus element, O is an oxygen element, 0.3 ≦ x ≦ 3, and 4 ≦ z ≦ 6.

  It is comprised from one of these.

  The second compound adopts one of the following crystal structures.

・ Hollandite structure
・ Rams delight structure
・ Anatase structure
・ Brookite structure
・ Pyroluth structure
・ ReO ₃ structure
・ MoO _1.5 PO ₄ structure
・ TiO _0.5 PO ₄ structure
・ FePO ₄ structure
・ ΒMnO2 structure
・ ΓMnO2 structure
・ ΛMnO2 structure.

  In addition, the electron Fermi level of the first compound is set lower than the Fermi level of the electron of the second compound. This is one of the conditions necessary for making the recording layer state reversible. Here, all the Fermi levels are values measured from the vacuum level.

  By using the recording layer as described above, with respect to the recording density, in principle, the Pbpsi class can be realized, and furthermore, low power consumption can be achieved.

2. Basic principles of recording / erasing / playback
(1) The basic principle of data recording / erasing / reproducing in the information recording / reproducing apparatus according to the first example of the present invention will be described.

FIG. 1 shows the structure of the recording unit.
Reference numeral 11 denotes an electrode layer, 12 denotes a recording layer, and 13A denotes an electrode layer (or a protective layer).

  Small white circles in the recording layer 12 represent diffusion ions, and large white circles represent anions (X ions). Small black circles represent transition element ions. Typically, diffusion ions correspond to A ions and transition element ions correspond to M ions.

  When a voltage is applied to the recording layer 12 to generate a potential gradient in the recording layer 12, some of the diffusion ions move in the crystal. Therefore, in the example of the present invention, the initial state of the recording layer 12 is an insulator (high resistance state), and for recording, the recording layer 12 is phase-shifted by a potential gradient to make the recording layer 12 conductive (low). Resistance state).

  First, for example, a state in which the potential of the electrode layer 13A is relatively lower than the potential of the electrode layer 11 is created. If the electrode layer 11 is set to a fixed potential (for example, ground potential), a negative potential may be applied to the electrode layer 13A.

  At this time, some of the diffusion ions in the recording layer 12 move to the electrode layer (cathode) 13A side, and the diffusion ions in the recording layer (crystal) 12 decrease relative to the anions. The diffused ions that have moved to the electrode layer 13A side receive electrons from the electrode layer 13A and precipitate as metal, so that the metal layer 14 is formed.

  Alternatively, for example, when there is an empty site that can be occupied by diffusion ions in the crystal structure of the recording layer 12 such as a spinel structure, the diffusion ions that have moved to the electrode layer 13A side fill the empty site on the electrode layer 13A side. Also good. Also in this case, in order to satisfy the neutral condition of the local charge, the diffusion ions receive electrons from the electrode layer 13A and behave like a metal.

  Inside the recording layer 12, the anions become excessive, and as a result, the valence of transition element ions in the recording layer 12 is increased. That is, since the recording layer 12 has electron conductivity due to carrier injection, recording (set operation) is completed.

  Reproduction can be easily performed by passing a current pulse through the recording layer 12 and detecting the resistance value of the recording layer 12. However, the current pulse needs to be a minute value that does not cause a resistance change of the material constituting the recording layer 12.

  The above process is a kind of electrolysis, and an oxidizing agent is generated by electrochemical oxidation on the electrode layer (anode) 11 side, and a reducing agent is generated by electrochemical reduction on the electrode layer (cathode) 13A side. Can be considered.

  For this reason, in order to return the recording state (low resistance state) to the initial state (high resistance state), for example, the recording layer 12 is Joule-heated by a large current pulse to promote the oxidation-reduction reaction of the recording layer 12. Good. That is, the recording layer 12 returns to the insulator due to the residual heat after the interruption of the large current pulse (reset operation).

  Alternatively, the reset operation can be performed by applying an electric field in the opposite direction to that at the time of setting. That is, if the electrode layer 11 is set to a fixed potential as in the setting, a positive potential may be applied to the electrode layer 13A. Then, in addition to the oxidation-reduction reaction by Joule heat, the metal layer in the vicinity of the electrode layer 13A is oxidized and becomes a cation, and returns to the base structure due to the potential gradient in the recording layer 12. As a result, the transition element ion whose valence has increased is reduced to the same value as before the setting, and thus returns to the initial insulator.

  However, in order to put this operating principle into practical use, it must be confirmed that the reset operation does not occur at room temperature (a sufficiently long retention time is ensured) and that the power consumption of the reset operation is sufficiently small.

  The former can be dealt with by setting the valence of the diffusion ions to 2 or more.

  If the diffusion ions are monovalent like Li ions, a sufficient ion movement resistance cannot be obtained in the set state, and the diffusion ion elements immediately return from the metal layer 14 into the recording layer 12. . In other words, a sufficiently long retention time cannot be obtained.

  Further, if the diffusion ions are trivalent or higher, the voltage required for the set operation increases, and in the worst case, it may cause crystal collapse.

  Therefore, it is preferable for the information recording / reproducing apparatus that the valence of the diffusion ions (A ions) is divalent.

  For the latter, by using a structure in which the ion radius of the diffusion ions is optimized and a movement path exists so that the diffusion ions can move in the recording layer (crystal) 12 without causing crystal destruction. Yes. Such a recording layer 12 may employ the elements and crystal structures already described.

  In particular, in the spinel structure, it is known that the movement of cations is easy, and it is preferably used as the recording layer 12. However, even in such a spinel structure, it is necessary to optimize the combination of A ions and M ions in order to repeatedly and stably cause switching (ion movement).

In the spinel structure represented by the chemical formula AM ₂ X ₄ , an example in which A ions correspond to diffusion ions in FIG. 1 and M ions correspond to transition element ions in FIG. 1 will be described.

  In the spinel structure, as shown in FIG. 26, a phenomenon (inversion) in which sites where A ions and M ions exist is reported, and this degree is called an inversion parameter.

  When the inversion parameter is large, there is a high probability that M ions are present in the movement path of A ions when viewed as a whole crystal. This makes it easier to replace ions and M ions.

  Such inversion is likely to occur when the crystal is exposed to a high temperature. Therefore, the inversion is likely to occur not only when the film is formed but also when the recording layer is heated by Joule heat during the set / reset operation.

  Since A ion and M ion have different ionic radii and bond strength with anion (X ion), the lattice is distorted each time such ion exchange occurs, and the possibility that the crystal structure is destroyed increases. .

  Therefore, in order to repeatedly and stably cause a phase change, it is preferable to select a combination of A ions and M ions so that the inversion parameter becomes zero.

  If the inversion parameter is not 0, the position may be switched between A ions and M ions when the recording layer is held in the high resistance state phase or the low resistance state phase for a long time.

  Since the conductivity of spinel greatly depends on the hybrid orbit formed by M ions and X ions, the resistance in each phase changes when such inversion occurs. That is, if the inversion is large, there is a problem that the thermal stability of the resistance of the recording layer is low.

  Further, generally, the diffusion coefficient (easy to move) of ions in the crystal varies depending on the ion species, and the energy required for the oxidation / reduction reaction also varies depending on the ion species. Therefore, when inversion occurs, the degree to which the A ions move locally varies, and as a result, there arises a problem that the resistance in each resistance state phase varies.

  That is, in order to cause resistance change repeatedly and stably, it is preferable to select a combination of A ions and M ions so that the inversion parameter becomes zero.

  When oxygen O is used as X, it is known that a group IIb may be used as the A ion in order to reduce the inversion. Therefore, it is preferable to use Zn, Cd, or Hg as the A ion.

  On the other hand, it is preferable to use a Va group, a VIa group, or a VIIa group as an M ion that forms a host structure for movement of A ions together with X ions.

  It is reported that the inversion parameter is almost 0 in these combinations, but the inversion parameter does not become 0 in other ZnFe2O4, MgCr2O4, and the like.

  Furthermore, in order to ensure sufficient ion mobility, it is preferable to use Zn having a small ion radius as the A ion. The effect of inversion is more prominent as the element size is smaller and the recording layer thickness is smaller.

  On the other hand, conditions suitable for the atomic species used as M ions further include the following.

  That is, there are two points: a low resistance state when A ions are extracted, and a stable structure after the A ions are extracted.

  This is because if the structure after the movement of the A ion is not stably maintained, the site where the A ion returns is lost, and the set / reset cannot be stably repeated.

In order that the structure from which the A ion is extracted is stable and the Joule heat generated at the time of setting and resetting does not significantly affect the base structure, the compound represented by the chemical formula M ₂ X ₄ (equal to MX ₂ ) is stable. The presence thereof is preferable because neutral conditions of local charges can be satisfied.

When oxygen O is used as X, it is preferable to use group VIa or group VIIa as the M ion because a conductive crystal represented by the chemical formula MO ₂ exists. VO ₂ using a group Va atom exhibits a metal-insulator transition near room temperature, and its characteristics may vary depending on the operating temperature.

  From the above considerations, in order to cause switching repeatedly and stably, Zn, Cd, and Hg are used as the A ion elements so that the inversion parameter is small and the matrix structure is thermally stable, and the M ions are the main component ions. It is preferable to use Cr, Mo, W, Mn, Tc, and Re as the (Mm ion) element.

  Further preferred examples of atomic species used as M ions will be shown.

Even when it stably exists in the state indicated by MO ₂ , the interval between the M ions and the O ions varies depending on the valence of the M ions, and therefore the crystal lattice of the recording layer 12 is slightly distorted when the set / reset operation is performed. It will be.

In addition, when MO ₂ exists as a crystal having a λMnO ₂ structure, which is a structure after A ions are removed from the spinel structure, it is easy to keep the crystal structure constant regardless of the presence or absence of A ions.

Therefore, it is more preferable to use the VIIa group, which is known to form a crystal having a λMnO ₂ structure, as the M ion, since the relative change in the ionic radius due to the change in valence is small.

  That is, it is more preferable to use Mn, Tc, and Re as the Mm ion element. Furthermore, considering the ease of control of the electronic state in the crystal, Mn having a small ion radius is most preferable as the Mm ion element.

  Further, as a more preferable configuration, it is known that a part of the Mm ion element may be substituted with a substitution ion (Ms ion) element in order to buffer the distortion of the lattice.

  As examples of the Ms ion element suitably used for such a purpose, Zn, Fe, Co, Ni, Al, Ga and the like are known.

  Among these, when Al, which is an element that is not a transition element, is used as the Ms ion element, if the A ion adjacent to Al moves, the neutral condition of the charge is not satisfied in the vicinity of Al. End up.

  Therefore, the movement of A ions hardly occurs in the vicinity of Al, and as a result, the change in the lattice spacing hardly occurs in the vicinity of Al. For this reason, it is possible to prevent the entire recording layer from being distorted.

  By preventing the entire recording layer from being distorted in this way, it is possible to avoid the crystal structure of the recording layer from being destroyed by a phase change, and therefore, further improvement in repeated resistance can be expected. When Mn is used as the Mm ion element, since the ionic radius is close, it is most preferable to use Al as the Ms ion element.

  Finally, the optimum value of the mixing ratio of each atom will be described.

  When there are empty sites that can be occupied by A ions, or when A ions can occupy sites originally occupied by M ions, the mixing ratio of A ions is somewhat arbitrary.

  Therefore, the mixing ratio of A ions was set to 0.1 ≦ x ≦ 2.2. In practice, it is possible to optimize the mixing ratio of A ions so that the resistance in each state or the diffusion coefficient of A ions becomes an optimum value.

  If the mixing ratio of A ions is too small, it is difficult to stably produce and maintain the structure, and if the mixing ratio of A ions is too large, diffusion of A ions becomes difficult. Therefore, it is more preferable that 0.5 ≦ x ≦ 1.5.

  With respect to M ions (Mm ions and Ms ions), if the mixing ratio exceeds 2, it must be located at a site originally occupied by A ions, which makes diffusion of A ions difficult.

  On the other hand, if the total amount of ions occupying the M ion site is too small, it becomes difficult to stably maintain the structure after the A ions are extracted.

  Accordingly, the mixing ratio of M ions is preferably 1.5 ≦ y ≦ 2. As described later, it is more preferable that 1.8 ≦ y ≦ 2 except that the A ion can occupy the M ion site.

  Next, the substitution amount of Ms ions = (Ms ions) / (Mm ions + Ms ions) will be described.

  First, if the Ms ion exceeds the mixing amount of the Mm ion, the effect of selecting the Mm ion is weakened so that repeated switching can be stably performed. Therefore, the substitution amount is preferably smaller than 0.5.

  Furthermore, if the Ms ions are not uniformly dispersed in the M ions, there is a difference in the ease of movement of the A ions depending on the position, resulting in a difference in resistance value. Therefore, the Ms ions must be uniformly dispersed. is there. For this purpose, the substitution amount is more preferably smaller than about 0.4.

  On the other hand, if the mixing amount of Ms ions is too small, the effect of adding Ms ions cannot be obtained sufficiently. Therefore, if Ms ions are intentionally used, the substitution amount is more preferably 0.1 or more.

  Accordingly, the substitution amount ≦ 0.5 is preferable, and 0.1 ≦ substitution amount ≦ 0.4 is more preferable.

  Unlike the case of using as a secondary battery, not all A ions are moved. Therefore, when a suitable combination of A ions and Mm ions is used, the Ms ions can be reduced by optimizing the voltage pulse conditions. Even when not used, it is possible to obtain a recording layer in which resistance changes repeatedly and stably.

  For example, when Zn is used as the A ion element and Mn is used as the Mm ion element, the Mn ratio is slightly smaller than 2 and the mixture ratio is such that the M ion site cannot be filled. It is also possible to obtain a replacement effect.

  Therefore, when Zn is used as the A ion element and Mn is used as the Mm ion element, the effect of buffering the lattice distortion can be provided by adjusting the mixing ratio without using substitution ions.

  Although the case where a sufficiently large crystal is obtained has been described with reference to FIG. 1, the mechanism described in the present invention can be applied to the case where the crystal is divided in the film thickness direction as shown in FIG. Thus, the movement of the A ion and the accompanying resistance change can occur.

  That is, when a negative voltage is applied to the electrode layer 13 with the electrode layer 11 grounded, a potential gradient is generated in the recording layer 12 and A ions are transported. When the A ions move to the crystal interface, they gradually receive electrons from a region close to the electrode layer 13A and behave like a metal. As a result, a metal layer 14 is formed in the vicinity of the crystal interface.

  Further, since the valence of the transition element ions is increased inside the recording layer 12, the conductivity thereof is increased. In such a case, since a conductive path of the metal layer is formed along the crystal interface, the resistance between the electrode layer 11 and the electrode layer 13 decreases, and the element changes to a low resistance state phase.

  Also in this case, it is possible to change to the high resistance state phase by pulling back the A ions at the crystal interface into the spinel structure by Joule heating by a large current pulse or application of a reverse voltage pulse.

  However, in order for the diffusion ions to move efficiently as shown in FIG. 1 with respect to the applied voltage, it is preferable that the direction in which the diffusion ions diffuse and the direction in which the electric field is applied coincide.

  In the case of the spinel structure, as shown in FIG. 1, when the recording layer is oriented in the (011) direction, the moving path is arranged substantially parallel to the electric field direction, so the recording layer is oriented in the (011) direction. It is preferable.

  The film thickness of the recording layer can be appropriately set so that the resistance in the high resistance state phase and the low resistance state phase has desired values, but is typically 1 nm or more and 500 nm or less. When the recording area is reduced, it is more preferable that the recording area is smaller than 10 times the recording area in order to prevent the recording layer from spreading in the in-plane direction.

  By the way, since an oxidizing agent is generated on the electrode layer (anode) 11 side after the setting operation, the electrode layer 11 is made of a material that is not easily oxidized (for example, electrically conductive nitride, electrically conductive oxide, etc.). It is preferable.

  Moreover, as such a material, the thing which does not have ion conductivity is good.

Examples of such a material include those shown below. Among them, LaNiO ₃ can be said to be the most preferable material from the viewpoint of comprehensive performance in consideration of good electrical conductivity and the like.

・ MN
M is at least one element selected from the group consisting of Ti, Zr, Hf, V, Nb, and Ta. N is nitrogen.

・ MO _x
M is selected from the group of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Hf, Ta, W, Re, Ir, Os, Pt At least one element. The molar ratio x shall satisfy 1 ≦ x ≦ 4.

・ AMO ₃
A is at least one element selected from the group consisting of La, K, Ca, Sr, Ba, and Ln (Lanthanide).

  M is selected from the group of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Hf, Ta, W, Re, Ir, Os, Pt At least one element.

  O is oxygen.

A ₂ MO ₄
A is at least one element selected from the group of K, Ca, Sr, Ba, and Ln (Lanthanide).

  M is selected from the group of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Hf, Ta, W, Re, Ir, Os, Pt At least one element.

  O is oxygen.

  In addition, since a reducing agent is generated on the protective layer (cathode) 13 side after the setting operation, the protective layer 13 preferably has a function of preventing the recording layer 12 from reacting with the atmosphere.

Examples of such a material include semiconductors such as amorphous carbon, diamond-like carbon, and SnO ₂ .

  The electrode layer 13A may function as a protective layer for protecting the recording layer 12, or a protective layer may be provided instead of the electrode layer 13A. In this case, the protective layer may be an insulator or a conductor.

In order to efficiently heat the recording layer 12 in the reset operation, a heater layer (a material having a resistivity of about 10 ⁻⁵ Ωcm or more) may be provided on the cathode side, here, on the electrode layer 13A side.

  (2) The basic principle of recording / erasing / reproducing information in the information recording / reproducing apparatus according to the second example of the present invention will be described.

FIG. 2 shows the structure of the recording unit.
Reference numeral 11 denotes an electrode layer, 12 denotes a recording layer, and 13A denotes an electrode layer (or a protective layer).

  The recording layer 12 is disposed on the electrode layer 11 side, and is disposed on the electrode layer 13A side with the first compound 12A represented by AxM1yX1z, and has at least one kind of transition element. The cation element of the first compound 12A And a second compound 12B having a void site that can accommodate the.

  The small white circles indicated by bold lines in the first compound 12A represent transition element ions (typically M1 ions), the small white circles in the first compound 12A represent diffusion ions (typically A ions), and the second compound. A black circle in 12B represents a transition element ion (M2 ion). A large circle represents an anion (X1 ion in the first compound 12A and X2 ion in the second compound 12B).

  As shown in FIG. 3, the first and second compounds 12A and 12B constituting the recording unit 12 may be stacked in a plurality of two or more layers.

  In such a recording section, when a potential gradient is generated in the recording layer 12 by applying a potential to the electrode layers 11 and 13A so that the first compound 12A is on the anode side and the second compound 12B is on the cathode side, A part of the diffusion ions in the compound 12A moves in the crystal and enters the second compound 12B on the cathode side.

  In the crystal of the second compound 12B, there are void sites that can accommodate the diffusion ions. Therefore, the diffusion ions that have moved from the first compound 12A are accommodated in the void sites.

  Therefore, the valence of the transition element ions in the first compound 12A increases, and the valence of the transition element ions in the second compound 12B decreases.

  That is, assuming that the first and second compounds 12A and 12B are in the high resistance state (insulator) in the initial state (reset state), some of the diffused ions in the first compound 12A are the second compound 12B. By moving in, conductive carriers are generated in the crystals of the first and second compounds 12A and 12B, and both of them have electrical conductivity.

  As described above, by applying the current / voltage pulse to the recording layer 12, the electric resistance value of the recording layer 12 is reduced, so that the set operation (recording) is realized.

  At the same time, electrons move from the first compound 12A toward the second compound 12B, but the electron Fermi level of the second compound 12B is higher than the electron Fermi level of the first compound 12A. The total energy of the recording layer 12 increases.

  Further, even after the set operation is completed, such a high energy state is continued, so that the recording layer 12 may naturally return from the set state (low resistance state) to the reset state (high resistance state). There is sex.

  However, such a concern can be avoided by using the recording layer 12 according to the example of the present invention. That is, the set state can be maintained.

  This is because so-called ion movement resistance works.

  It is the valence of the diffusion ions in the first compound 12A that plays this role. It is very important that this valence is divalent.

  If the diffusion ions are monovalent elements such as Li ions, sufficient ion migration resistance cannot be obtained in the set state, and the diffusion ions immediately return from the second compound 12B to the first compound 12A. End up. In other words, a sufficiently long retention time cannot be obtained.

  In addition, if the diffusion ions are trivalent or higher elements, the voltage required for the set operation increases, and in the worst case, it may cause crystal collapse.

  Accordingly, it is preferable for the information recording / reproducing apparatus to set the valence of the diffusion ions to two.

  By the way, since the oxidizing agent is generated on the anode side after the setting operation is completed, in this case as well, the electrode layer 11 is difficult to be oxidized and does not have ionic conductivity (for example, electrically conductive oxidation). Are preferably used. Suitable examples thereof are as described above.

  The reset operation (erasing) may be performed by heating the recording layer 12 and promoting the phenomenon that the diffused ions stored in the void sites of the second compound 12B return to the first compound 12A.

  Specifically, the recording layer 12 can be easily returned to the original high resistance state (insulator) by using Joule heat generated by applying a large current pulse to the recording layer 12 and its residual heat. it can.

  As described above, by applying a large current pulse to the recording layer 12, the electrical resistance value of the recording layer 12 is increased, so that a reset operation (erasing) is realized. Alternatively, the reset operation can be performed by applying an electric field in the opposite direction to that at the time of setting.

  Here, in order to realize low power consumption, it is important to use a structure in which the ion radius of the diffusion ions is optimized and a movement path exists so that the diffusion ions can move within the crystal without causing crystal destruction. become.

  When the material and the crystal structure described in the overview item are used as the second compound 12B, it is effective to satisfy such conditions and realize low power consumption.

  Further, in the compounds represented by Chemical Formulas 1 to 3 having a structure as shown in FIG. 1, cation movement easily occurs, and therefore, it is suitable for use as the first compound.

  In particular, in the spinel structure, it is known that cation movement is easy, and it is preferably used as the first compound.

  In the case of using oxide spinel, at least one material selected from the group of Zn, Cd, and Hg as the diffusing ion element and from the group of Cr, Mo, W, Mn, Tc, and Re as the transition element. It is preferable to use at least one selected material, and a part of the transition element may be appropriately replaced with at least one element selected from the group of Fe, Co, Ni, Al, and Ga. As a result, it is possible to switch repeatedly and stably as described above.

Further, as the second compound that is preferably used in combination with such a spinel material, it is preferable to use M2X2 ₂ having a λMnO ₂ structure in view of ease of cation movement and degree of coincidence of lattice constants. The case where Ti is used as M2 and O is used as X2 is most preferable.

  A suitable range of the film thickness of the second compound will be described.

  In order to obtain the effect of storing diffused ions by the void sites, the film thickness of the second compound is preferably 1 nm or more.

  On the other hand, if the number of void sites in the second compound is larger than the number of diffused ions in the first compound, the resistance change effect of the second compound is reduced, so the number of void sites in the second compound is the same. It is preferable that the number of diffusion ions in the first compound in the cross-sectional area is the same as or less than that.

  Since the density of the diffused ions in the first compound and the density of the void sites in the second compound are substantially the same, the film thickness of the second compound is preferably the same as or smaller than the film thickness of the first compound. .

In general, a heater layer (a material having a resistivity of about 10 ⁻⁵ Ωcm or more) for further promoting the reset operation may be provided on the cathode side.

  In the probe memory, since a reducing material is deposited on the cathode side, it is preferable to provide a surface protective layer in order to prevent reaction with the atmosphere.

The heater layer and the surface protective layer can be formed of one material having both functions. For example, semiconductors such as amorphous carbon, diamond-like carbon, and SnO ₂ have both a heater function and a surface protection function.

  Reproduction can be easily performed by passing a current pulse through the recording layer 12 and detecting the resistance value of the recording layer 12.

  However, the current pulse needs to be a minute value that does not cause a resistance change of the material constituting the recording layer 12.

3. Embodiment
Next, some preferred embodiments will be described.
Below, the example of this invention is demonstrated about the case where it applies to a probe memory, and the case where it applies to a semiconductor memory.

(1) Probe memory
A. Structure
4 and 5 show a probe memory according to an example of the present invention.

  A recording medium is disposed on the XY scanner 14. A probe array is arranged to face the recording medium.

  The probe array includes a substrate 23 and a plurality of probes (heads) 24 arranged in an array on one surface side of the substrate 23. Each of the plurality of probes 24 is constituted by a cantilever, for example, and is driven by multiplex drivers 25 and 26.

  Each of the plurality of probes 24 can be individually operated using the microactuator in the substrate 23. Here, an example will be described in which all of the probes 24 are collectively operated to access the data area of the recording medium. .

  First, using the multiplex drivers 25 and 26, all the probes 24 are reciprocated in the X direction at a constant cycle, and the position information in the Y direction is read from the servo area of the recording medium. The position information in the Y direction is transferred to the driver 15.

  The driver 15 drives the XY scanner 14 based on this position information, moves the recording medium in the Y direction, and positions the recording medium and the probe.

  When the positioning of both is completed, data reading or writing is performed simultaneously and continuously on all the probes 24 on the data area.

  Data reading and writing are continuously performed because the probe 24 reciprocates in the X direction. Data reading and writing are performed line by line in the data area by sequentially changing the position of the recording medium in the Y direction.

  Note that the recording medium may be reciprocated in the X direction at a constant period to read position information from the recording medium, and the probe 24 may be moved in the Y direction.

  The recording medium includes, for example, a substrate 20, an electrode layer 21 on the substrate 20, and a recording layer 22 on the electrode layer 21.

  The recording layer 22 has a plurality of data areas and servo areas arranged at both ends of the plurality of data areas in the X direction. The plurality of data areas occupy the main part of the recording layer 22.

  A servo burst signal is recorded in the servo area. The servo burst signal indicates position information in the Y direction within the data area.

  In addition to these pieces of information, an address area for recording address data and a preamble area for synchronization are arranged in the recording layer 22.

  The data and servo burst signal are recorded on the recording layer 22 as recording bits (electric resistance fluctuation). The “1” and “0” information of the recording bit is read by detecting the electric resistance of the recording layer 22.

  In this example, one probe (head) is provided corresponding to one data area, and one probe is provided for one servo area.

  The data area is composed of a plurality of tracks. A track in the data area is specified by an address signal read from the address area. The servo burst signal read from the servo area is used to move the probe 24 to the center of the track and eliminate the recording bit reading error.

  Here, by making the X direction correspond to the down-track direction and the Y direction correspond to the track direction, it becomes possible to use the head position control technology of the HDD.

B. Recording / playback operation
The recording / reproducing operation of the probe memory shown in FIGS. 4 and 5 will be described.

FIG. 6 shows a state during recording (set operation).
The recording medium is composed of an electrode layer 21 on a substrate (for example, a semiconductor chip) 20, a recording layer 22 on the electrode layer 21, and a protective layer 13B on the recording layer 22. The protective layer 13B is made of, for example, a thin insulator.

  The recording operation is performed by applying a voltage to the surface of the recording bit 27 of the recording layer 22 and generating a potential gradient inside the recording bit 27. Specifically, a current / voltage pulse may be given to the recording bit 27.

First Example The first example is a case where the material shown in FIG. 1 is used for the recording layer.

  First, as shown in FIG. 7, a state in which the potential of the probe 24 is relatively lower than the potential of the electrode layer 21 is created. If the electrode layer 21 is set to a fixed potential (for example, ground potential), a negative potential may be applied to the probe 24.

  The current pulse is generated by emitting electrons from the probe 24 toward the electrode layer 21 using, for example, an electron generation source or a hot electron source. Alternatively, the voltage pulse may be applied by bringing the probe 24 into contact with the surface of the recording bit 27.

  At this time, for example, in the recording bit 27 of the recording layer 22, some of the diffused ions move to the probe (cathode) 24 side, and the cations in the crystal decrease relative to the anions. The diffused ions that have moved to the probe 24 side receive electrons from the probe 24 and are deposited as metal. Alternatively, if there is an empty site that can be occupied by diffusion ions, that site may be occupied.

  In the recording bit 27, the anion becomes excessive, and as a result, the valence of the transition element ion in the recording bit 27 is increased. That is, since the recording bit 27 has electron conductivity due to carrier injection due to phase change, the resistance in the film thickness direction decreases, and recording (set operation) is completed.

  Note that the current pulse for recording can also be generated by creating a state in which the potential of the probe 24 is relatively higher than the potential of the electrode layer 21.

FIG. 8 shows the reproduction.
Reproduction is performed by passing a current pulse through the recording bit 27 of the recording layer 22 and detecting the resistance value of the recording bit 27. However, the current pulse is set to a minute value so that the material constituting the recording bit 27 of the recording layer 22 does not change in resistance.

  For example, a read current (current pulse) generated by the sense amplifier S / A is passed from the probe 24 to the recording bit 27, and the resistance value of the recording bit 27 is measured by the sense amplifier S / A.

If the material according to the example of the present invention is used, a difference in resistance value between the set / reset states of 10 ³ or more can be secured.

  In reproduction, continuous reproduction is possible by scanning the recording medium with the probe 24 (scanning).

  The erase (reset) operation is performed by heating the recording bit 27 of the recording layer 22 with a large current pulse to promote the redox reaction in the recording bit 27. Alternatively, a pulse that gives a potential difference in the opposite direction to that in the set operation may be applied.

  The erasing operation can be performed for each recording bit 27, or can be performed in units of a plurality of recording bits 27 or blocks.

Second Example The second example is a case where the material shown in FIG. 2 is used for the recording layer.

  First, as shown in FIG. 9, a state is created in which the potential of the probe 24 is relatively lower than the potential of the electrode layer 21. If the electrode layer 21 is set to a fixed potential (for example, ground potential), a negative potential may be applied to the probe 24.

  At this time, a part of the diffusion ions in the first compound (anode side) 12A of the recording layer 22 moves in the crystal and falls in the void sites of the second compound (cathode side) 12B. Along with this, the valence of the transition element ions in the first compound 12A increases, and the valence of the transition element ions in the second compound 12B decreases. As a result, conductive carriers are generated in the crystals of the first and second compounds 12A and 12B, and both of them have electrical conductivity.

  Thereby, the set operation (recording) is completed.

  Regarding the recording operation, if the positional relationship between the first and second compounds 12A and 12B is reversed, the setting operation may be performed with the potential of the probe 24 relatively higher than the potential of the electrode layer 21. it can.

FIG. 10 shows a state during reproduction.
The reproduction operation is performed by passing a current pulse through the recording bit 27 and detecting the resistance value of the recording bit 27. However, the current pulse is set to a minute value that does not cause a resistance change of the material constituting the recording bit 27.

For example, a read current (current pulse) generated by the sense amplifier S / A is passed from the probe 24 to the recording layer (recording bit) 22 and the resistance value of the recording bit is measured by the sense amplifier S / A. If the new material described above is adopted, the difference in resistance value between the set / reset states can be secured at 10 ³ or more.

  The reproduction operation can be continuously performed by scanning the probe 24.

  The reset (erase) operation uses Joule heat generated by flowing a large current pulse to the recording layer (recording bit) 22 and its residual heat, and diffused ions are transferred from the void sites in the second compound 12B to the first compound. What is necessary is just to promote the effect | action which is going to return in 12A. Alternatively, a pulse that gives a potential difference in the opposite direction to that in the set operation may be applied.

  The erasing operation can be performed for each recording bit 27, or can be performed in units of a plurality of recording bits 27 or blocks.

C. Summary
According to such a probe memory, higher recording density and lower power consumption can be realized than the current hard disk or flash memory.

(2) Semiconductor memory
A. Structure
FIG. 11 shows a cross-point type semiconductor memory according to an example of the present invention.

  Word lines WLi−1, WLi, and WLi + 1 extend in the X direction, and bit lines BLj−1, BLj, and BLj + 1 extend in the Y direction.

  One end of the word lines WLi-1, WLi, WLi + 1 is connected to the word line driver & decoder 31 via a MOS transistor RSW as a selection switch, and one end of the bit lines BLj-1, BLj, BLj + 1 is used as a selection switch. The bit line driver & decoder & read circuit 32 is connected via the MOS transistor CSW.

  Selection signals Ri-1, Ri, Ri + 1 for selecting one word line (row) are inputted to the gate of the MOS transistor RSW, and one bit line (column) is inputted to the gate of the MOS transistor CSW. Selection signals Ci-1, Ci, Ci + 1 are input to select.

  Memory cell 33 is arranged at the intersection of word lines WLi-1, WLi, WLi + 1 and bit lines BLj-1, BLj, BLj + 1. This is a so-called cross-point cell array structure.

  The memory cell 33 is provided with a diode 34 for preventing a sneak current during recording / reproduction.

  FIG. 12 shows the structure of the memory cell array portion of the semiconductor memory of FIG.

  On the semiconductor chip 30, word lines WLi-1, WLi, WLi + 1 and bit lines BLj-1, BLj, BLj + 1 are arranged, and memory cells 33 and diodes 34 are arranged at intersections of these wirings.

  The feature of such a cross-point cell array structure is that it is advantageous for high integration because it is not necessary to individually connect a MOS transistor to the memory cell 33. For example, as shown in FIGS. 14 and 15, it is possible to stack the memory cells 33 to make the memory cell array have a three-dimensional structure.

  For example, as shown in FIG. 13, the memory cell 33 includes a stack structure of a recording layer 22, a protective layer 13 </ b> B, and a heater layer 35. One memory cell 33 stores 1-bit data. The diode 34 is disposed between the word line WLi and the memory cell 33.

B. Recording / playback operation
The recording / reproducing operation will be described with reference to FIGS.
Here, it is assumed that the memory cell 33 surrounded by the dotted line A is selected, and the recording / reproducing operation is executed for this.

First Example The first example is a case where the material shown in FIG. 1 is used for the recording layer.

  In recording (set operation), it is only necessary to apply a voltage to the selected memory cell 33 and generate a potential gradient in the memory cell 33 to flow a current pulse. For example, the potential of the word line WLi is set to the bit line BLj. It creates a state that is relatively lower than the potential. If the bit line BLj is set to a fixed potential (eg, ground potential), a negative potential may be applied to the word line WLi.

  At this time, in the selected memory cell 33 surrounded by the dotted line A, some of the diffused ions move to the word line (cathode) WLi side, and the cations in the crystal decrease relative to the negative ions. . The diffused ions that have moved to the word line WLi side receive electrons from the word line WLi and are deposited as metal.

  In the selected memory cell 33 surrounded by the dotted line A, the anion becomes excessive, and as a result, the valence of the transition element ion in the crystal is increased. That is, since the selected memory cell 33 surrounded by the dotted line A has electron conductivity due to carrier injection due to phase change, recording (set operation) is completed.

  During recording, it is preferable that the unselected word lines WLi−1 and WLi + 1 and the unselected bit lines BLj−1 and BLj + 1 are all biased to the same potential.

  In standby before recording, it is preferable to precharge all the word lines WLi-1, WLi, WLi + 1 and all the bit lines BLj-1, BLj, BLj + 1.

  The current pulse for recording may be generated by creating a state in which the potential of the word line WLi is relatively higher than the potential of the bit line BLj.

  Reproduction is performed by passing a current pulse through the selected memory cell 33 surrounded by the dotted line A and detecting the resistance value of the memory cell 33. However, the current pulse needs to be a minute value that does not cause a resistance change of the material constituting the memory cell 33.

For example, a read current (current pulse) generated by the read circuit is passed from the bit line BLj to the memory cell 33 surrounded by the dotted line A, and the resistance value of the memory cell 33 is measured by the read circuit. If the new material already explained is adopted, the difference in resistance value between the set / reset states can be secured at 10 ³ or more.

  The erase (reset) operation is performed by heating the selected memory cell 33 surrounded by the dotted line A with a large current pulse to promote the oxidation-reduction reaction in the memory cell 33.

Second Example The second example is a case where the material shown in FIG. 2 is used for the recording layer.

  In the recording operation (set operation), it is only necessary to apply a voltage to the selected memory cell 33 and generate a potential gradient in the memory cell 33 to flow a current pulse. For example, the potential of the word line WLi is set to the bit line. It is relatively lower than the potential of BLj. If the bit line BLj is set to a fixed potential (eg, ground potential), a negative potential may be applied to the word line WLi.

  At this time, in the selected memory cell 33 surrounded by the dotted line A, some of the diffusion ions in the first compound move to the void site of the second compound. For this reason, the valence of the transition element ions in the first compound increases, and the valence of the transition element ions in the second compound decreases. As a result, conductive carriers are generated in the crystals of the first and second compounds, and both have electrical conductivity.

  Thereby, the set operation (recording) is completed.

  During recording, it is preferable that the unselected word lines WLi−1 and WLi + 1 and the unselected bit lines BLj−1 and BLj + 1 are all biased to the same potential.

  In standby before recording, it is preferable to precharge all the word lines WLi-1, WLi, WLi + 1 and all the bit lines BLj-1, BLj, BLj + 1.

  The current pulse may be generated by creating a state in which the potential of the word line WLi is relatively higher than the potential of the bit line BLj.

  The reproduction operation is performed by passing a current pulse through the selected memory cell 33 surrounded by the dotted line A and detecting the resistance value of the memory cell 33. However, the current pulse needs to be a minute value that does not cause a resistance change of the material constituting the memory cell 33.

For example, a read current (current pulse) generated by the read circuit is passed from the bit line BLj to the memory cell 33 surrounded by the dotted line A, and the resistance value of the memory cell 33 is measured by the read circuit. If the new material already explained is adopted, the difference in resistance value between the set / reset states can be secured at 10 ³ or more.

  The reset (erase) operation uses Joule heat generated by flowing a large current pulse to the selected memory cell 33 surrounded by the dotted line A and its residual heat, so that the diffuse ion element becomes a void in the second compound. What is necessary is just to accelerate | stimulate the effect | action which is going to return in a 1st compound from a site.

C. Summary
According to such a semiconductor memory, it is possible to realize higher recording density and lower power consumption than current hard disks and flash memories.

(3) Other
In this embodiment, the probe memory and the semiconductor memory have been described. However, the material and principle proposed in the example of the present invention can be applied to a recording medium such as a current hard disk.

4). Production method
A method for manufacturing a recording medium according to an example of the present invention will be described.

Here, the structure of the recording medium shown in FIG. 6 is taken as an example.
The substrate 20 is a disk made of glass and having a diameter of about 60 mm and a thickness of about 1 mm. An electrode layer 21 is formed on such a substrate 20 by depositing Pt (platinum) to a thickness of about 500 nm.

First, an atmosphere having a temperature of 300 to 600 ° C., Ar (argon) 95%, and O 2 (oxygen) 5% is used on the electrode layer 21 by using a target whose composition is adjusted so that ZnMn ₂ O ₄ is deposited. Among them, RF magnetron sputtering is performed to form ZnMn ₂ O ₄ having a thickness of about 10 nm constituting a part of the recording layer 22.

Subsequently, TiO ₂ having a thickness of about 3 nm is formed on ZnMn ₂ O ₄ by RF magnetron sputtering. As a result, the recording layer 22 has a laminated structure of ZnMn ₂ O ₄ and TiO ₂ .

  Finally, if the protective layer 13B is formed on the recording layer 22, a recording medium as shown in FIG. 6 is completed.

5. Experimental example
A description will be given of an experimental example in which several samples were prepared and the resistance difference between the reset (erase) state and the set (write) state was evaluated.

  As a sample, a recording medium having the structure shown in FIG. 6 is used.

  For the evaluation, a probe pair whose tip diameter is sharpened to 10 nm or less is used.

  The probe pair is brought into contact with the protective layer 13B, and writing / erasing is performed using one of them. Writing is performed by applying a voltage pulse of 1 V to the recording layer 22 with a width of 10 nsec, for example. Erasing is performed by applying a voltage pulse of 0.2 V to the recording layer 22 with a width of, for example, 100 nsec.

  Also, reading is performed using the other one of the probe pair between the writing / erasing. Reading is performed by applying a voltage pulse of 0.1 V with a width of 10 nsec to the recording layer 22 and measuring the resistance value of the recording layer (recording bit) 22.

(1) First experiment example
Samples of the first experimental example are as follows.

The electrode layer 21 is a Pt film formed on the disk with a thickness of about 500 nm. The recording layer 22 is made of ZnV ₂ O ₄ and the protective layer 13B is made of diamond-like carbon (DLC).

For example, ZnV ₂ O ₄ maintains the temperature of the disk at a value in the range of 300 ° C. to 600 ° C. and performs RF magnetron sputtering in an atmosphere of Ar 95% and O ₂ 5%. It is formed with a thickness of about 10 nm. The diamond-like carbon is formed with a thickness of about 3 nm on ZnV ₂ O ₄ by, for example, a CVD method.

The resistance value after writing was on the order of 10 ³ Ω, and the resistance value after erasing was on the order of 10 ⁷ Ω. The difference in resistance between them was about 10 ⁴ Ω, and it was confirmed that a sufficient margin for reading could be secured.

(2) Second experiment example
In the second experimental example, the same sample as the first experimental example is used except that the recording layer is made of ZnCr ₂ O ₄ .

The resistance value after programming / erasing is 10 ³ Ω / 10 ⁷ Ω in the same way as the first experimental example, and the resistance difference between the two is about 10 ⁴ Ω, confirming that a sufficient margin can be secured for reading. It was done.

(3) Third experiment example
In the third experimental example, the same sample as the first experimental example is used except that the recording layer is made of ZnMn ₂ O ₄ .

The resistance value after programming / erasing is 10 ³ Ω / 10 ⁷ Ω in the same way as the first experimental example, and the resistance difference between the two is about 10 ⁴ Ω, confirming that a sufficient margin can be secured for reading. It was done.

(4) Fourth experiment example
In the fourth experimental example, the same sample as the first experimental example is used except that the recording layer is made of ZnCo ₂ O ₄ .

The resistance value after programming / erasing is 10 ³ Ω / 10 ⁷ Ω in the same way as the first experimental example, and the resistance difference between the two is about 10 ⁴ Ω, confirming that a sufficient margin can be secured for reading. It was done.

(5) Fifth experimental example
In the fifth experimental example, the same sample as the first experimental example is used except that the recording layer is MgCr ₂ O ₄ .

The resistance value after programming / erasing is 10 ³ Ω / 10 ⁷ Ω in the same way as the first experimental example, and the resistance difference between the two is about 10 ⁴ Ω, confirming that a sufficient margin can be secured for reading. It was done.

(6) Sixth experimental example
In the sixth experimental example, the same sample as the first experimental example is used except that the recording layer is MgMn ₂ O ₄ .

The resistance value after programming / erasing is 10 ³ Ω / 10 ⁷ Ω in the same way as the first experimental example, and the resistance difference between the two is about 10 ⁴ Ω, confirming that a sufficient margin can be secured for reading. It was done.

(7) Seventh experimental example
In the seventh experimental example, the same sample as the first experimental example is used except that the recording layer is MgCo ₂ O ₄ .

The resistance value after programming / erasing is 10 ³ Ω / 10 ⁷ Ω in the same way as the first experimental example, and the resistance difference between the two is about 10 ⁴ Ω, confirming that a sufficient margin can be secured for reading. It was done.

(8) Eighth experimental example
In the eighth experimental example, the same sample as the first experimental example is used except that the recording layer is CoMn ₂ O ₄ .

The resistance value after programming / erasing is 10 ³ Ω / 10 ⁷ Ω in the same way as the first experimental example, and the resistance difference between the two is about 10 ⁴ Ω, confirming that a sufficient margin can be secured for reading. It was done.

(9) Ninth experiment example
In the ninth experimental example, the same sample as the first experimental example is used except that the recording layer is CaCr ₂ O ₄ .

The resistance value after programming / erasing is 10 ³ Ω / 10 ⁷ Ω in the same way as the first experimental example, and the resistance difference between the two is about 10 ⁴ Ω, confirming that a sufficient margin can be secured for reading. It was done.

(10) 10th experiment example
In the tenth experimental example, the same sample as the first experimental example is used except that the recording layer is CaMn ₂ O ₄ .

The resistance value after programming / erasing is 10 ³ Ω / 10 ⁷ Ω in the same way as the first experimental example, and the resistance difference between the two is about 10 ⁴ Ω, confirming that a sufficient margin can be secured for reading. It was done.

(11) 11th experiment example
In the eleventh experimental example, the same sample as the first experimental example is used except that the recording layer is SrMn ₂ O ₄ .

The resistance value after programming / erasing is 10 ³ Ω / 10 ⁷ Ω in the same way as the first experimental example, and the resistance difference between the two is about 10 ⁴ Ω, confirming that a sufficient margin can be secured for reading. It was done.

(12) 12th experimental example
In the twelfth experimental example, the same sample as that of the first experimental example is used except that the recording layer is a laminate of Ba _0.25 Mn ₂ O ₄ and Ba. Ba _0.25 Mn ₂ O ₄ is formed by sputtering, and Ba is formed with a thickness of about 10 nm.

The resistance value after programming / erasing is 10 ³ Ω / 10 ⁷ Ω in the same way as the first experimental example, and the resistance difference between the two is about 10 ⁴ Ω, confirming that a sufficient margin can be secured for reading. It was done.

(13) Example 13
In the thirteenth experimental example, the same sample as the first experimental example is used, except that the recording layer is made of a laminate of Zn _0.25 Mn ₂ O ₄ and Zn. Zn _0.25 Mn ₂ O ₄ is formed by sputtering, and Zn is formed with a thickness of about 10 nm.

The initial resistance value was on the order of 10 ⁸ Ω, while the resistance value after writing was on the order of 10 ³ Ω, and the resistance value after erasing was on the order of 10 ⁷ Ω. The resistance difference between writing and erasing was 10 ⁴ Ω to 10 ⁵ Ω, and it was confirmed that a sufficient margin could be secured for reading.

(14) 14th experimental example
In the fourteenth experimental example, the same sample as the first experimental example is used except that the recording layer is CuAlO ₂ .

The initial resistance value was on the order of 10 ⁸ Ω, while the resistance value after writing was on the order of 10 ³ Ω, and the resistance value after erasure was on the order of 10 ⁶ Ω. The resistance difference between writing and erasing is 10 ³ Ω to 10 ⁵ Ω, and it was confirmed that a sufficient margin can be secured for reading.

(15) 15th experimental example
In the fifteenth experimental example, the same sample as the first experimental example is used except that the recording layer is MgCrO ₃ .

The initial resistance value was on the order of 10 ⁷ Ω, while the resistance value after writing was on the order of 10 ³ Ω, and the resistance value after erasure was on the order of 10 ⁶ Ω. The resistance difference between writing and erasing was 10 ³ Ω to 10 ⁴ Ω, and it was confirmed that a sufficient margin could be secured for reading.

(16) Example 16
In the sixteenth experimental example, the same sample as the first experimental example is used except that the recording layer is NiWN ₂ and the protective layer is SnO ₂ . NiWN ₂ is formed by sputtering in an atmosphere of Ar 95% and NH 35%.

The resistance value in the initial state was on the order of 10 ⁷ Ω, whereas the resistance value after writing was on the order of 10 ³ Ω, and the resistance value after erasure was on the order of 10 ⁵ Ω. The resistance difference between writing and erasing is 10 ² Ω to 10 ⁵ Ω, and it was confirmed that a sufficient margin can be secured for reading.

(17) 17th experiment example
In the seventeenth experimental example, the same sample as the first experimental example is used except that the recording layer is made of Zn _1.2 V _1.8 O ₄ and the protective layer is made of SnO ₂ .

The initial resistance value was on the order of 10 ⁶ Ω, while the resistance value after writing was on the order of 10 ² Ω, and the resistance value after erasing was on the order of 10 ⁶ Ω. The resistance difference between writing and erasing is about 10 ⁴ Ω, and it was confirmed that a sufficient margin can be secured for reading.

(18) Example 18
In the eighteenth experimental example, the same sample as the first experimental example is used except that the recording layer is made of Zn _1.2 Cr _1.8 O ₄ and the protective layer is made of SnO ₂ .

The initial resistance value was on the order of 10 ⁶ Ω, while the resistance value after writing was on the order of 10 ² Ω, and the resistance value after erasing was on the order of 10 ⁶ Ω. The resistance difference between writing and erasing is about 10 ⁴ Ω, and it was confirmed that a sufficient margin can be secured for reading.

(19) 19th experimental example
In the nineteenth experimental example, the same sample as the first experimental example is used except that the recording layer is made of ZnAl _1.8 Cr _0.2 O ₄ and the protective layer is made of SnO ₂ .

The resistance value in the initial state was on the order of 10 ⁸ Ω, whereas the resistance value after writing was on the order of 10 ³ Ω, and the resistance value after erasing was on the order of 10 ⁸ Ω. The resistance difference between writing and erasing is about 10 ⁵ Ω, and it was confirmed that a sufficient margin can be secured for reading.

(20) Example 20
In the twentieth experimental example, the same sample as the first experimental example is used except that the recording layer is made of ZnAl _1.8 Mn _0.2 O ₄ and the protective layer is made of SnO ₂ .

The resistance value in the initial state was on the order of 10 ⁸ Ω, whereas the resistance value after writing was on the order of 10 ³ Ω, and the resistance value after erasing was on the order of 10 ⁸ Ω. The resistance difference between writing and erasing is about 10 ⁵ Ω, and it was confirmed that a sufficient margin can be secured for reading.

(21) Example 21
In the twenty-first experimental example, the same sample as the first experimental example is used except that the recording layer is SiNi ₂ O ₄ and the protective layer is SnO ₂ .

The resistance value in the initial state was on the order of 10 ⁸ Ω, whereas the resistance value after writing was on the order of 10 ³ Ω, and the resistance value after erasing was on the order of 10 ⁸ Ω. The resistance difference between writing and erasing is about 10 ⁵ Ω, and it was confirmed that a sufficient margin can be secured for reading.

(22) Example 22
In the twenty- _second experimental example, the same sample as the first experimental example is used except that the recording layer is SeNi ₂ O ₄ and the protective layer is SnO ₂ .

The resistance value in the initial state was on the order of 10 ⁸ Ω, whereas the resistance value after writing was on the order of 10 ³ Ω, and the resistance value after erasing was on the order of 10 ⁸ Ω. The resistance difference between writing and erasing is about 10 ⁵ Ω, and it was confirmed that a sufficient margin can be secured for reading.

(23) Example 23
In the 23rd experimental example, the same sample as the first experimental example is used except that the recording layer is NiTiO ₃ and the protective layer is SnO ₂ .

The resistance value in the initial state was on the order of 10 ⁸ Ω, whereas the resistance value after writing was on the order of 10 ³ Ω, and the resistance value after erasing was on the order of 10 ⁸ Ω. The resistance difference between writing and erasing is about 10 ⁵ Ω, and it was confirmed that a sufficient margin can be secured for reading.

(24) 24th experimental example
The specifications of the sample of the 24th experimental example are as follows.
The recording layer 22 is composed of a laminated structure of ZnMn ₂ O ₄ having a thickness of about 10 nm and TiO ₂ having a thickness of about 3 nm.

In this case, the resistance value in the reset state was in the 10 ⁷ Ω range, and the resistance value in the set state was in the 10 ³ Ω range. In addition, it was confirmed that the cycle life could be over 100,000 cycles.

(25) 25th experimental example
The specifications of the sample of the 25th experimental example are as follows.
The recording layer 22 is composed of a laminated structure of ZnMn ₂ O ₄ having a thickness of about 10 nm and ZrO ₂ having a thickness of about 3 nm.

In this case, the resistance value in the reset state was in the 10 ⁷ Ω range, and the resistance value in the set state was in the 10 ³ Ω range. In addition, it was confirmed that the cycle life could be over 100,000 cycles.

(26) Example 26
The specifications of the sample of the 26th experimental example are as follows.
The recording layer 22 is composed of a laminated structure of MgMn ₂ O ₄ having a thickness of about 10 nm and TiO ₂ having a thickness of about 3 nm.

In this case, the resistance value in the reset state was in the 10 ⁷ Ω range, and the resistance value in the set state was in the 10 ³ Ω range. In addition, it was confirmed that the cycle life could be over 100,000 cycles.

(27) Example 27
The specifications of the sample of the 27th experimental example are as follows.
The recording layer 22 is composed of a laminated structure of MgMn ₂ O ₄ having a thickness of about 10 nm and ZrO ₂ having a thickness of about 3 nm.

In this case, the resistance value in the reset state was in the 10 ⁷ Ω range, and the resistance value in the set state was in the 10 ³ Ω range. In addition, it was confirmed that the cycle life could be over 100,000 cycles.

(28) Example 28
The specifications of the sample of the 28th experimental example are as follows.
The recording layer 22 is composed of a laminated structure of SrMoO ₃ having a thickness of about 10 nm and ReO ₃ having a thickness of about 3 nm.

In this case, the resistance value in the reset state was in the 10 ⁷ Ω range, and the resistance value in the set state was in the 10 ³ Ω range. In addition, it was confirmed that the cycle life could be over 100,000 cycles.

(29) 29th experimental example
The sample used in the 29th experimental example uses a recording medium having the structure shown in FIG. In this experimental example, the same sample as the first experimental example is used except that the recording layer is ZnMn ₂ O ₄ and the protective layer is SnO ₂ .

The resistance value after programming / erasing is in the order of 10 ³ Ω / 10 ⁷ Ω as in the first experimental example, and the resistance ratio of both is about 10 ⁴ , confirming that a sufficient margin can be secured for reading. It was. In this sample, after 10,000 cycles, the resistance value after writing / erasing was on the order of 10 ⁴ Ω / 10 ⁶ Ω, and more than 10,000 cycles could be realized.

(30) 30th experiment example
In the 30th experimental example, the same sample as the 29th experimental example is used except that the recording layer is made of ZnCr _1.7 Al _0.3 O ₄ .

The resistance value after programming / erasing is in the order of 10 ⁴ Ω / 10 ⁸ Ω as in the 29th experimental example, and the resistance ratio of both is about 10 ⁴ , confirming that a sufficient margin can be secured for reading. It was. In this sample, after 10,000 cycles, the resistance value after writing / erasing was on the order of 10 ⁴ Ω / 10 ⁷ Ω, and more than 10,000 cycles could be realized.

(31) 31st experimental example
In the 31st experimental example, the same sample as the 29th experimental example is used except that the recording layer is made of ZnMn _1.8 Al _0.2 O ₄ .

The resistance value after programming / erasing is in the order of 10 ⁴ Ω / 10 ⁸ Ω as in the 29th experimental example, and the resistance ratio of both is about 10 ⁴ , confirming that a sufficient margin can be secured for reading. It was. In this sample, after 10,000 cycles, the resistance value after writing / erasing was on the order of 10 ⁴ Ω / 10 ⁸ Ω, and more than 10,000 cycles could be realized.

(32) Example 32
In the 32nd experimental example, the same sample as the 29th experimental example is used except that the recording layer is made of ZnMn _1.6 Ni _0.4 O ₄ .

The resistance value after programming / erasing is in the order of 10 ⁴ Ω / 10 ⁸ Ω as in the 29th experimental example, and the resistance ratio of both is about 10 ⁴ , confirming that a sufficient margin can be secured for reading. It was. In this sample, after 10,000 cycles, the resistance value after writing / erasing was on the order of 10 ⁴ Ω / 10 ⁷ Ω, and more than 10,000 cycles could be realized.

(33) Example 33
In the 33rd experimental example, the same sample as the 29th experimental example is used except that the recording layer is made of Zn _1.1 Mn _1.9 O ₄ .

The resistance value after programming / erasing is in the order of 10 ⁴ Ω / 10 ⁷ Ω, as in the 29th experimental example, and the resistance ratio of both is about 10 ³ , confirming that a sufficient margin can be secured for reading. It was. In this sample, after 10,000 cycles, the resistance value after writing / erasing was on the order of 10 ⁴ Ω / 10 ⁷ Ω, and more than 10,000 cycles could be realized.

(34) Example 34
In the 34th experimental example, the same sample as the 29th experimental example is used except that RuO ₂ is used as the lower electrode and the recording layer is made of ZnMn ₂ O ₄ . RuO ₂ film formation is performed by RF magnetron sputtering in an atmosphere of temperature 600 ° C., argon 80%, oxygen 20% using a target whose composition is adjusted so that RuO ₂ is deposited. 200 nm. When RuO ₂ is used as the lower electrode instead of Pt, a ZnMn ₂ O ₄ film oriented in the (011) direction can be obtained due to lattice constant matching.

The resistance value after programming / erasing is 10 ² Ω / 10 ⁷ Ω in the same way as the 29th experimental example, and the resistance ratio of both is about 10 ⁵ , and it is confirmed that a sufficient margin can be secured for reading. It was. In this sample, after 10,000 cycles, the resistance value after writing / erasing was in the order of 10 ³ Ω / 10 ⁶ Ω, and more than 10,000 cycles could be realized.

(35) Example 35
The sample used in the 35th experimental example uses a recording medium having the structure shown in FIG. In this experimental example, the recording layer 22 uses ZnMn ₂ O ₄ with a thickness of 10 nm as the first compound and a laminated structure of TiO 2 with a thickness of 3 nm as the second compound. The protective layer and SnO _2.

The resistance value after programming / erasing is in the order of 10 ⁴ Ω / 10 ⁹ Ω as in the 29th experimental example, and the resistance ratio of both is about 10 ⁵ , confirming that a sufficient margin can be secured for reading. It was. In this sample, after 10,000 cycles, the resistance value after writing / erasing was on the order of 10 ⁴ Ω / 10 ⁸ Ω, and more than 10,000 cycles could be realized.

(36) Example 36
In the 36th experimental example, the same sample as the 35th experimental example is used except that the first compound is ZnCr _1.7 Al _0.3 O ₄ .

The resistance value after programming / erasing is 10 ⁵ Ω / 10/10 ¹⁰ Ω, as in the 29th experimental example, and the resistance ratio of both is about 10 ⁵ , confirming that a sufficient margin can be secured for reading. It was. In this sample, after 10,000 cycles, the resistance value after writing / erasing was on the order of 10 ⁵ Ω / 10 ⁹ Ω, and more than 10,000 cycles could be realized.

(37) 37th experimental example
In the 37th experimental example, the same sample as the 35th experimental example is used except that the first compound is ZnMn _1.8 Al _0.2 O ₄ .

The resistance value after programming / erasing is 10 ⁵ Ω / 10/10 ¹⁰ Ω, as in the 29th experimental example, and the resistance ratio of both is about 10 ⁵ , confirming that a sufficient margin can be secured for reading. It was. In this sample, after 10,000 cycles, the resistance value after writing / erasing was on the order of 10 ⁵ Ω / 10 ¹⁰ Ω, realizing over 10,000 cycles.

(38) Example 38
In the 38th experimental example, the same sample as the 35th experimental example is used except that the first compound is ZnMn _1.6 Ni _0.4 O ₄ .

The resistance value after programming / erasing is 10 ⁵ Ω / 10/10 ¹⁰ Ω, as in the 29th experimental example, and the resistance ratio of both is about 10 ⁵ , confirming that a sufficient margin can be secured for reading. It was. In this sample, after 10,000 cycles, the resistance value after writing / erasing was on the order of 10 ⁵ Ω / 10 ⁹ Ω, and more than 10,000 cycles could be realized.

(39) Example 39
In the 39th experimental example, the same sample as the 35th experimental example is used except that the first compound is Zn _1.1 Mn _1.9 O ₄ .

The resistance value after programming / erasing is in the 10 ⁵ Ω range / 10 ⁹ Ω level, similar to the 29th experimental example, and the resistance ratio of both is about 10 ⁴ , confirming that a sufficient margin can be secured for reading. It was. In this sample, after 10,000 cycles, the resistance value after writing / erasing was on the order of 10 ⁵ Ω / 10 ⁹ Ω, and more than 10,000 cycles could be realized.

(40) 40th experimental example
In the 40th experimental example, RuO ₂ is used as the lower electrode, and the same sample as the 35th experimental example is used except that the first compound is ZnMn ₂ O ₄ .

The resistance value after programming / erasing is in the order of 10 ³ Ω / 10 ⁹ Ω as in the 29th experimental example, and the resistance ratio of both is about 10 ⁶ , confirming that a sufficient margin can be secured for reading. It was. In this sample, after 10,000 cycles, the resistance value after writing / erasing was in the order of 10 ³ Ω / 10 ⁸ Ω, realizing over 10,000 cycles.

(41) Comparative example
In the comparative example, the same sample as the 29th experimental example is used except that the recording layer is made of MgO.

In this comparative example, writing / erasing could not be performed when a 10 ns, 3 V pulse was applied as in the 29th experimental example, so writing was performed by applying a 10 ns wide, 20 V pulse, and 1 μs Erasing was performed by applying a pulse of -3V in width. Resistance value after writing / erasing was 10 ⁵ Omega base / 10 ¹³ Omega stand. In this sample, the resistance value remained unchanged at 10 ³ Ω after 10,000 cycles.

  Thus, when MgO having a NaCl structure is used as the recording layer, since diffusion of cations is difficult to occur, a large voltage is required for writing / erasing, and the diffused ions are difficult to return to the original position. There is a disadvantage that it is inferior to repeated resistance.

(42) Summary
As described above, the basic operations of writing, erasing, and reading can be performed in any sample of the first to forty experimental examples.

Tables 1A to 1D summarize the verification results of the first to forty experimental examples and the comparative example.

6). Application to flash memory
(1) Structure
The example of the present invention can also be applied to a flash memory.

  FIG. 16 shows a memory cell of the flash memory.

  The memory cell of the flash memory is composed of a MIS (metal-insulator-semiconductor) transistor.

  A diffusion layer 42 is formed in the surface region of the semiconductor substrate 41. A gate insulating layer 43 is formed on the channel region between the diffusion layers 42. A recording layer (RRAM: Resistive RAM) 44 according to an example of the present invention is formed on the gate insulating layer 43. A control gate electrode 45 is formed on the recording layer 44.

  The semiconductor substrate 41 may be a well region, and the semiconductor substrate 41 and the diffusion layer 42 have opposite conductivity types. The control gate electrode 45 becomes a word line and is made of, for example, conductive polysilicon.

  The recording layer 44 is made of the material shown in FIG. 1, FIG. 2, or FIG.

(2) Basic operation
The basic operation will be described with reference to FIG.
The set (write) operation is performed by applying the potential V1 to the control gate electrode 45 and applying the potential V2 to the semiconductor substrate 41.

  The difference between the potentials V1 and V2 needs to be large enough for the recording layer 44 to undergo phase change or resistance change, but the direction is not particularly limited.

  That is, either V1> V2 or V1 <V2 may be used.

  For example, assuming that the recording layer 44 is an insulator (high resistance) in the initial state (reset state), the gate insulating layer 43 is substantially thickened, so that the threshold value of the memory cell (MIS transistor) is reached. Get higher.

  If the recording layer 44 is changed to a conductor (low resistance) by applying the potentials V1 and V2 from this state, the gate insulating layer 43 is substantially thinned. Therefore, the threshold value of the memory cell (MIS transistor) is , Get lower.

  Although the potential V2 is applied to the semiconductor substrate 41, the potential V2 may be transferred from the diffusion layer 42 to the channel region of the memory cell instead.

  The reset (erase) operation is performed by applying the potential V1 'to the control gate electrode 45, applying the potential V3 to one of the diffusion layers 42, and applying the potential V4 (<V3) to the other of the diffusion layers 42.

  The potential V1 'is set to a value exceeding the threshold value of the memory cell in the set state.

  At this time, the memory cell is turned on, electrons flow from one side of the diffusion layer 42 to the other side, and hot electrons are generated. Since the hot electrons are injected into the recording layer 44 through the gate insulating layer 43, the temperature of the recording layer 44 rises.

  As a result, the recording layer 44 changes from a conductor (low resistance) to an insulator (high resistance), so that the gate insulating layer 43 is substantially thickened, and the threshold value of the memory cell (MIS transistor) is , Get higher.

  As described above, the threshold value of the memory cell can be changed based on a principle similar to that of the flash memory. Therefore, the information recording / reproducing apparatus according to the example of the present invention can be put into practical use by using the technology of the flash memory.

(3) NAND flash memory
FIG. 17 shows a circuit diagram of the NAND cell unit. FIG. 18 shows the structure of a NAND cell unit according to an example of the present invention.

  An N-type well region 41b and a P-type well region 41c are formed in the P-type semiconductor substrate 41a. A NAND cell unit according to an example of the present invention is formed in the P-type well region 41c.

  The NAND cell unit is composed of a NAND string composed of a plurality of memory cells MC connected in series, and a total of two select gate transistors ST connected to the both ends one by one.

  The memory cell MC and the select gate transistor ST have the same structure. Specifically, these include an N-type diffusion layer 42, a gate insulating layer 43 on a channel region between the N-type diffusion layers 42, a recording layer (RRAM) 44 on the gate insulating layer 43, and a recording layer 44. And the upper control gate electrode 45.

  The state (insulator / conductor) of the recording layer 44 of the memory cell MC can be changed by the basic operation described above. On the other hand, the recording layer 44 of the select gate transistor ST is fixed in a set state, that is, a conductor (low resistance).

  One of the select gate transistors ST is connected to the source line SL, and the other one is connected to the bit line BL.

  It is assumed that all memory cells in the NAND cell unit are in a reset state (resistance is large) before the set (write) operation.

  The set (write) operation is sequentially performed one by one from the memory cell MC on the source line SL side to the memory cell on the bit line BL side.

  V1 (plus potential) is applied to the selected word line (control gate electrode) WL as a write potential, and Vpass is applied to the unselected word line WL as a transfer potential (a potential at which the memory cell MC is turned on).

  The select gate transistor ST on the source line SL side is turned off, the select gate transistor ST on the bit line BL side is turned on, and program data is transferred from the bit line BL to the channel region of the selected memory cell MC.

  For example, when the program data is “1”, a write inhibit potential (for example, the same potential as V1) is transferred to the channel region of the selected memory cell MC, and the recording layer 44 of the selected memory cell MC is transferred. The resistance value should not change from a high state to a low state.

  When the program data is “0”, V2 (<V1) is transferred to the channel region of the selected memory cell MC, and the resistance value of the recording layer 44 of the selected memory cell MC is changed from a high state to a low state. To change.

  In the reset (erase) operation, for example, V1 'is applied to all the word lines (control gate electrodes) WL, and all the memory cells MC in the NAND cell unit are turned on. Further, the two select gate transistors ST are turned on, V3 is applied to the bit line BL, and V4 (<V3) is applied to the source line SL.

  At this time, since hot electrons are injected into the recording layers 44 of all the memory cells MC in the NAND cell unit, a reset operation is collectively executed for all the memory cells MC in the NAND cell unit.

  In the read operation, a read potential (plus potential) is applied to the selected word line (control gate electrode) WL, and the memory cell MC receives data “0”, “1” on the unselected word line (control gate electrode) WL. A potential to be turned on without fail is given.

  Further, the two select gate transistors ST are turned on to supply a read current to the NAND string.

  When a read potential is applied to the selected memory cell MC, the selected memory cell MC is turned on or off according to the value of the data stored therein. For example, data can be read by detecting a change in the read current. it can.

  In the structure of FIG. 18, the select gate transistor ST has the same structure as the memory cell MC. For example, as shown in FIG. 19, the select gate transistor ST is not formed with a recording layer. A normal MIS transistor can also be used.

  FIG. 20 shows a modification of the NAND flash memory.

  This modification is characterized in that the gate insulating layers of the plurality of memory cells MC constituting the NAND string are replaced with a P-type semiconductor layer 47.

  When the high integration progresses and the memory cell MC is miniaturized, the P-type semiconductor layer 47 is filled with a depletion layer without applying a voltage.

  At the time of setting (writing), a positive write potential (for example, 3.5 V) is applied to the control gate electrode 45 of the selected memory cell MC, and a positive transfer potential (to the control gate electrode 45 of the non-selected memory cell MC). For example, give 1V).

  At this time, the surface of the P-type well region 41c of the plurality of memory cells MC in the NAND string is inverted from P-type to N-type, and a channel is formed.

  Therefore, as described above, the set operation can be performed by turning on the select gate transistor ST on the bit line BL side and transferring the program data “0” from the bit line BL to the channel region of the selected memory cell MC. it can.

  For example, reset (erase) is performed by applying a negative erase potential (for example, −3.5 V) to all the control gate electrodes 45 and applying a ground potential (0 V) to the P-type well region 41 c and the P-type semiconductor layer 47. This can be performed collectively for all the memory cells MC constituting the NAND string.

  At the time of reading, a positive read potential (for example, 0.5 V) is applied to the control gate electrode 45 of the selected memory cell MC, and the memory cell MC receives data “0” to the control gate electrode 45 of the non-selected memory cell MC. A transfer potential (for example, 1 V) that is always turned on regardless of “1” is applied.

  However, the threshold voltage Vth ”1” of the memory cell MC in the “1” state is in the range of 0V <Vth ”1” <0.5V, and the threshold voltage Vth ”0 of the memory cell MC in the“ 0 ”state "" Is assumed to be in the range of 0.5V <Vth "0" <1V.

  Further, the two select gate transistors ST are turned on to supply a read current to the NAND string.

  In such a state, since the amount of current flowing through the NAND string changes according to the value of the data stored in the selected memory cell MC, data can be read by detecting this change.

  In this modification, the hole doping amount of the P-type semiconductor layer 47 is larger than that of the P-type well region 41c, and the Fermi level of the P-type semiconductor layer 47 is 0.5 than that of the P-type well region 41c. It is desirable that the depth is about V.

  This is because when a positive potential is applied to the control gate electrode 45, inversion from the P-type to N-type starts from the surface portion of the P-type well region 41c between the N-type diffusion layers 42, and a channel is formed. It is for doing so.

  Thus, for example, at the time of writing, the channel of the non-selected memory cell MC is formed only at the interface between the P-type well region 41c and the P-type semiconductor layer 47, and at the time of reading, a plurality of memories in the NAND string is formed. The channel of the cell MC is formed only at the interface between the P-type well region 41 c and the P-type semiconductor layer 47.

  That is, even if the recording layer 44 of the memory cell MC is a conductor (set state), the diffusion layer 42 and the control gate electrode 45 are not short-circuited.

(4) NOR flash memory
FIG. 21 shows a circuit diagram of the NOR cell unit. FIG. 22 shows the structure of a NOR cell unit according to an example of the present invention.

  An N-type well region 41b and a P-type well region 41c are formed in the P-type semiconductor substrate 41a. A NOR cell according to an example of the present invention is formed in the P-type well region 41c.

  The NOR cell is composed of one memory cell (MIS transistor) MC connected between the bit line BL and the source line SL.

  The memory cell MC includes an N-type diffusion layer 42, a gate insulating layer 43 on a channel region between the N-type diffusion layers 42, a recording layer (RRAM) 44 on the gate insulating layer 43, and a control on the recording layer 44. And a gate electrode 45.

  The state (insulator / conductor) of the recording layer 44 of the memory cell MC can be changed by the basic operation described above.

(5) Two-tra type flash memory
FIG. 23 shows a circuit diagram of a two-tracell unit. FIG. 24 shows the structure of a two-tracell unit according to an example of the present invention.

  The 2-tra cell unit has been recently developed as a new cell structure that combines the characteristics of a NAND cell unit and the characteristics of a NOR cell.

  An N-type well region 41b and a P-type well region 41c are formed in the P-type semiconductor substrate 41a. In the P-type well region 41c, the two tracell unit according to the example of the present invention is formed.

  The two tracell unit is composed of one memory cell MC and one select gate transistor ST connected in series.

  The memory cell MC and the select gate transistor ST have the same structure. Specifically, these include an N-type diffusion layer 42, a gate insulating layer 43 on a channel region between the N-type diffusion layers 42, a recording layer (RRAM) 44 on the gate insulating layer 43, and a recording layer 44. And the upper control gate electrode 45.

  The state (insulator / conductor) of the recording layer 44 of the memory cell MC can be changed by the basic operation described above. On the other hand, the recording layer 44 of the select gate transistor ST is fixed in a set state, that is, a conductor (low resistance).

  Select gate transistor ST is connected to source line SL, and memory cell MC is connected to bit line BL.

  The state (insulator / conductor) of the recording layer 44 of the memory cell MC can be changed by the basic operation described above.

  In the structure of FIG. 24, the select gate transistor ST has the same structure as that of the memory cell MC. For example, as shown in FIG. 25, the select gate transistor ST is usually formed without forming a recording layer. It is also possible to use a MIS transistor.

7). Other
According to the example of the present invention, recording (writing) is performed only at a site (recording unit) to which an electric field is applied using a change in conductivity due to a change in the valence of the transition element ions, and thus extremely fine. Data can be recorded in the area with extremely low power consumption.

  Erasing is performed by applying heat. However, if the material proposed in the example of the present invention is used, the structure of the oxide hardly changes, so that erasing can be performed with low power consumption.

  Alternatively, erasing can also be performed by applying an electric field in the direction opposite to that during recording, and if the material proposed in the example of the present invention is used, erasing can be performed without dissipating thermal energy, so that it is extremely small Erasing is possible with power consumption.

  Furthermore, according to the example of the present invention, the conductor portion is formed in the insulator after writing, so that current is concentrated on the conductor portion during reading, and the sensing efficiency is improved. An extremely high recording principle can be realized.

  Furthermore, according to the example of the present invention, it is possible to record and erase repeatedly and stably by combining a cation that easily moves and a transition element ion that keeps the matrix structure stable.

  As described above, according to the example of the present invention, it is possible to record data with a recording density that cannot be achieved by the prior art, despite the extremely simple mechanism. Therefore, the example of the present invention has a great industrial advantage as a next generation technology that breaks down the recording density barrier of the current nonvolatile memory.

  The example of the present invention is not limited to the above-described embodiment, and can be embodied by modifying each component without departing from the scope of the invention. Various inventions can be configured by appropriately combining a plurality of constituent elements disclosed in the above-described embodiments. For example, some constituent elements may be deleted from all the constituent elements disclosed in the above-described embodiments, or constituent elements of different embodiments may be appropriately combined.

The figure which shows the recording principle. The figure which shows the recording principle. The figure which shows the recording principle. The figure which shows the probe memory which concerns on the example of this invention. The figure which shows a recording medium. The figure which shows the mode at the time of the recording of a probe memory. The figure which shows write-in operation | movement. The figure which shows read-out operation | movement. The figure which shows write-in operation | movement. The figure which shows read-out operation | movement. 1 is a diagram showing a semiconductor memory according to an example of the present invention. The figure which shows the example of a memory cell array structure. The figure which shows the example of a memory cell structure. The figure which shows the example of a memory cell array structure. The figure which shows the example of a memory cell array structure. The figure which shows the example of application to flash memory. The circuit diagram which shows a NAND cell unit. The figure which shows the structure of a NAND cell unit. The figure which shows the structure of a NAND cell unit. The figure which shows the structure of a NAND cell unit. The circuit diagram which shows a NOR cell. The figure which shows the structure of a NOR cell. The circuit diagram which shows 2 tracell units. The figure which shows the structure of 2 tracell units. The figure which shows the structure of 2 tracell units. The figure explaining the inversion in a spinel structure. The figure which shows the principle of recording / reproduction | regeneration.

Explanation of symbols

  11, 13A: Electrode layer, 12, 22: Recording layer, 13B: Protective layer, 14: XY scanner, 15: Driver, 20, 23, 30: Substrate, 21: Electrode layer, 24: Probe, 25, 26: Multi Plex driver, 27: recording bit, 31: word line driver & decoder, 32: bit line driver & decoder & readout circuit, 33: memory cell, 34: diode, 35: heater layer, WLi-1, WLi, WLi + 1: word Line, BLj-1, BLj, BLj + 1: Bit line.

Claims (12)

A recording layer, and means for recording information by applying a voltage to the recording layer to cause a resistance change in the recording layer, the recording layer comprising:
i. layer although made of a first compound expressed by A x M1 y X1 z, A, M1 is cation element, X1 is at least one element O, S, Se, N, Cl, Br, selected from I, 0.1 ≦ x ≦ 2.2, 0.5 ≦ y ≦ 2.5, 1.5 ≦ z ≦ 4.5.
ii. at least one transition element, and a layer made of a second compound having a vacant site that can accommodate the cation element
An information recording / reproducing apparatus characterized by including a structure in which layers are stacked . The second compound is
Chemical formula 4: xM2X2 ₂
Where □ is a void site in which the cation element is accommodated, M2 is Ti, Ge, Sn, V, Cr, Mn, Fe, Co, Ni, Nb, Ta, Mo, W, Re, Ru, Rh X2 is at least one element selected from O, S, Se, N, Cl, Br, and I, and 0.3 ≦ x ≦ 1.
Chemical formula 5: □ xM2X2 ₃
Where □ is a void site in which the cation element is accommodated, M2 is Ti, Ge, Sn, V, Cr, Mn, Fe, Co, Ni, Nb, Ta, Mo, W, Re, Ru, Rh X2 is at least one element selected from O, S, Se, N, Cl, Br, and I, and 1 ≦ x ≦ 2.
Chemical formula 6: □ xM2X2 ₄
Where □ is a void site in which the cation element is accommodated, M2 is Ti, Ge, Sn, V, Cr, Mn, Fe, Co, Ni, Nb, Ta, Mo, W, Re, Ru, Rh X2 is at least one element selected from O, S, Se, N, Cl, Br, and I, and 1 ≦ x ≦ 2.
Chemical formula 7: xM2POz
Where □ is a void site in which the cation element is accommodated, M2 is Ti, Ge, Sn, V, Cr, Mn, Fe, Co, Ni, Nb, Ta, Mo, W, Re, Ru, Rh At least one element selected from: P is a phosphorus element, O is an oxygen element, 0.3 ≦ x ≦ 3, and 4 ≦ z ≦ 6.
The information recording / reproducing apparatus according to claim 1 , wherein the information recording / reproducing apparatus is one of the above. The second compound includes a hollandite structure, a ramsdellite structure, an anatase structure, a brookite structure, a pyroloose structure, a ReO ₃ structure, a MoO _1.5 PO ₄ structure, a TiO _0.5 PO ₄ structure and a FePO ₄ structure, a βMnO2 structure, a γMnO2 structure, and a λMnO2 structure. The information recording / reproducing apparatus according to claim 1, wherein one of the information recording / reproducing apparatus is provided. 4. The information recording / reproducing apparatus according to claim 1 , wherein a Fermi level of electrons of the first compound is lower than a Fermi level of electrons of the second compound. 5. The first compound has chemical formula 1: A _x M1 _y X1 ₄ (0.1 ≦ x ≦ 2.2, 1.5 ≦ y ≦ 2), chemical formula 2: A _x M1 _y X1 ₃ (0.5 ≦ x ≦ 1.1, 0.9 ≦ y). ≦ 1) and Chemical Formula 3: A _x M1 _y X1 ₄ (0.5 ≦ x ≦ 1.1, 0.9 ≦ y ≦ 1)
i. However, regarding Chemical Formula 1 and Chemical Formula 2, A is Na, K, Rb, Be, Mg, Ca, Sr, Ba, Al, Ga, Mn, Fe, Co, Ni, Cu, Zn, Si, P, At least one element selected from the group of S, Se, Ge, Ag, Au, Cd, Sn, Sb, Pt, Pd, Hg, Tl, Pb, Bi, M1 is Al, Ga, Ti, Ge, It is at least one element selected from the group consisting of Sn, V, Cr, Mn, Fe, Co, Ni, Nb, Ta, Mo, W, Tc, Re, Ru, and Rh.
ii. In addition, regarding chemical formula 3, A is Na, K, Rb, Be, Mg, Ca, Sr, Ba, Al, Ga, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Si , P, S, Se, Ge, Ag, Au, Cd, Sn, Sb, Pt, Pd, Hg, Tl, Pb, Bi, at least one element, M1 is Al, Ga, Ti , Ge, Sn, V, Nb, Ta, Cr, Mn, Mo, W, Ir, and Os.
iii. Further, regarding Chemical Formula 1, Chemical Formula 2, and Chemical Formula 3, A and M1 are different elements from each other, and X1 is at least one element selected from the group of O and N.
The first compound is selected from a spinel structure, a cryptomelane structure, an ilmenite structure, a malocite structure, a hollandite structure, a heterolite structure, a ramsdellite structure, a delafossite structure, an α-NaFeO ₂ structure, and a LiMoN ₂ structure. The information recording / reproducing apparatus according to claim 1 , wherein the information recording / reproducing apparatus has a crystal structure. The first compound has a spinel structure represented by Formula 1.
In Formula 1,
A is at least one element selected from the group of Zn, Cd, Hg,
M1 is at least one transition element selected from the group of Cr, Mo, W, Mn, Tc, Re,
6. The information recording / reproducing apparatus according to claim 5 , wherein X1 is O. In Formula 1,
7. The information recording / reproducing apparatus according to claim 6 , wherein M1 includes at least one element selected from the group of Fe, Co, Ni, Al, and Ga in addition to the transition element. The information recording / reproducing apparatus according to claim 1, wherein the first compound is (011) oriented. The information recording / reproducing apparatus according to claim 1 , wherein the means includes a head that locally applies the voltage to the recording layer. The information recording / reproducing apparatus according to claim 1 , wherein the means includes a word line and a bit line sandwiching the recording layer. 7. The device according to claim 1 , wherein the means includes a MIS transistor, and the recording layer is disposed between a gate electrode and a gate insulating layer of the MIS transistor. Information recording / reproducing apparatus. The means includes two second conductivity type diffusion layers in the first conductivity type semiconductor substrate, a first conductivity type semiconductor layer on the first conductivity type semiconductor substrate between the two second conductivity type diffusion layers, and And a gate electrode for controlling conduction / non-conduction between the two second conductivity type diffusion layers, and the recording layer is disposed between the gate electrode and the first conductivity type semiconductor layer. The information recording / reproducing apparatus according to any one of claims 1 to 6 .

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