Two-terminal switching element having bidirectional switching characteristic, resistive memory cross-point array including same, and method for manufacturing two-terminal switching element and cross-point resistive memory array
11043536 · 2021-06-22
Assignee
Inventors
- Jinpyo Hong (Seoul, KR)
- Yooncheol Bae (Seoul, KR)
- Ahrham Lee (Gimhae-si, KR)
- Gwangho BAEK (Incheon, KR)
Cpc classification
H10B61/00
ELECTRICITY
H10B63/80
ELECTRICITY
H10N70/826
ELECTRICITY
H10B61/10
ELECTRICITY
H10B63/20
ELECTRICITY
H10N70/011
ELECTRICITY
H10N70/24
ELECTRICITY
International classification
Abstract
Provided are a two-terminal switching element having a bidirectional switching characteristic, a resistive memory cross-point array including the same, and methods for manufacturing the two-terminal switching element and the cross-point resistive memory array. The two-terminal switching element includes a first electrode and a second electrode. A pair of first conductive metal oxide semiconductor layers electrically connected to the first electrode and the second electrode, respectively, is provided. A second conductive metal oxide semiconductor layer is disposed between the first conductive metal oxide semiconductor layers. Therefore, the two-terminal switching element can show a symmetrical and bidirectional switching characteristic.
Claims
1. A resistive memory cross-point array comprising: a plurality of first data lines; a plurality of second data lines crossing the first data lines; a switching layer disposed between each of the first data lines and each of the second data lines at a point at which each of the first data lines and each of the second data lines cross and including a pair of P-type metal oxide semiconductor layers and an N-type metal oxide semiconductor layer disposed between the pair of P-type metal oxide semiconductor layers, wherein the N-type metal oxide semiconductor layer has a smaller thickness than each of the P-type metal oxide semiconductor layers; and a bipolar variable resistive memory layer disposed between the switching layer and the second data line, wherein the P-type metal oxide semiconductor layers are CoOx (1.3<x<1.5) layers, and the N-type metal oxide semiconductor layer is InGaZnO and wherein the thickness of the N-type metal oxide semiconductor is 1 nm to 5 nm and the thickness of each of the P-type metal oxide semiconductor layers is 10 nm to 30 nm.
2. The array of claim 1, wherein the bipolar variable resistive memory layer is a magnetic tunnel junction (MTJ) structure or a resistance change memory layer.
3. The array of claim 1, further comprising an intermediate electrode located between the switching layer and the bipolar variable resistive memory layer.
4. The array of claim 1, wherein the P-type metal oxide semiconductor layer is CoOx (x=1.4).
5. The array of claim 1, wherein the P-type metal oxide semiconductor layer has a band gap of 1 to 2 eV.
Description
DESCRIPTION OF DRAWINGS
(1)
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MODES OF THE INVENTION
(10) Hereinafter, in order to further specifically describe the invention, exemplary embodiments of the present invention will be described in more detail with reference to the accompanying drawings. However, the invention is not limited to the above-described embodiments, and may be embodied in different forms.
(11) In this specification, it will be understood that when a layer is referred to as being disposed “on” another layer or a substrate, it can be directly formed on the other layer or the substrate, or a third layer can be interposed therebetween. Further, in this specification, it will be understood that orientational terms such as “upper side,” “upper (portion),” or “upper surface” used herein may also be understood to refer to a “lower side,” “lower (portion),” “lower surface,” “side,” “side (portion),” or “side surface.” That is, spatially orientational terms should be understood to refer to relative orientations but should not be understood to refer to absolute orientations for purposes of limitation. In addition, in this specification, terms such as “first” or “second” do not limit components, and will be understood only as terms distinguishing components.
(12) Further, thicknesses of layers and areas are exaggerated for clarity in the drawings of this specification. The same reference numerals indicate the same components throughout the specification.
(13)
(14) Referring to
(15) When a voltage having a predetermined absolute value or more is applied between the first electrode 100 and the second electrode 300, a depletion layer may be formed throughout the second conductivity type metal oxide semiconductor layer 220. In this case, a current may be conducted in a portion to which a reverse bias is applied among side surfaces of the second conductivity type metal oxide semiconductor layer 220, which are in contact with the first conductivity type metal oxide semiconductor layers 210 and 230. As a result, the two-terminal switching element may be turned on and may have both a threshold voltage having a positive value and a threshold voltage having a negative value, and thus bidirectional switching may be implemented.
(16) Meanwhile, the second conductivity type metal oxide semiconductor layer 220 may have a smaller thickness than each of the first conductivity type metal oxide semiconductor layers 210 and 230. In this case, an absolute value of the threshold voltage may be reduced. Each of the first conductivity type metal oxide semiconductor layers 210 and 230 may have a thickness in a range of 10 nm to 100 nm, and preferably, a thickness of 30 nm or less. Further the second conductivity type metal oxide semiconductor layer 220 may have a thickness in a range of 1 nm to 20 nm, and preferably a thickness of 5 nm or less.
(17) The first conductivity type metal oxide semiconductor layers 210 and 230 may be a lower metal oxide semiconductor layer 210 having a first conductivity type and an upper metal oxide semiconductor layer 230 having a first conductivity type. The lower and upper metal oxide semiconductor layers 210 and 230 may be the same material layer, and may have substantially the same thickness. In this case, the symmetry of the two-terminal switching element may be improved. However, the lower and upper metal oxide semiconductor layer 210 and 230 are not limited thereto, and may be different materials when the lower metal oxide semiconductor layer 210 having a first conductivity type and the upper metal oxide semiconductor layer 230 having a first conductivity type have the same conductivity type. Alternatively, the lower metal oxide semiconductor layer 210 having a first conductivity type and the upper metal oxide semiconductor layer 230 having a first conductivity type may have different thicknesses.
(18) When the first conductivity type metal oxide semiconductor layers 210 and 230 are P-type metal oxide semiconductor layers, the second conductivity type metal oxide semiconductor layer 220 may be an N-type metal oxide semiconductor layer. On the other hand, when the first conductivity type metal oxide semiconductor layers 210 and 230 are the N-type metal oxide semiconductor layers, the second conductivity type metal oxide semiconductor layer 220 may be the P-type metal oxide semiconductor layer. In this case, as an example, the P-type metal oxide semiconductor layers may each be one metal oxide layer selected from the group consisting of NiO.sub.x (1.1<x≤1.5), FeO.sub.x (1.1<x≤1.5), CoO.sub.x (1.1<x≤1.5), PdO.sub.x (1.1<x≤1.5), CuAlO.sub.x (1.8≤x<3), CuGaO.sub.x (1.8≤x<3), SrCu.sub.2O.sub.x (1≤x<1.8), RhO.sub.x(1.1<x≤1.5), CrO.sub.x (1.1<x≤1.5), CuO.sub.x (1.1<x≤1.5), Cu.sub.xO (1.5<x≤2), SnO.sub.x (1.1<x≤1.5), Ag.sub.xO (1.5<x≤2), LaMnO.sub.x (2.5<x≤3), YBaCu.sub.2O.sub.x (3.5<x≤4), PCMO (PrCaMnO.sub.3), LCMO (LaCaMnO.sub.3), LSMO (LaSrMnO.sub.3), and PZTO (PbZrTiO.sub.3). Meanwhile, the N-type metal oxide semiconductor layers may each be one metal oxide layer selected from the group consisting of ZnO, SnO.sub.2, In.sub.2O.sub.3, Ga.sub.2O.sub.3, InSnO, GaInO, ZnInO, ZnSnO, InGaZnO, TiO.sub.2, CeO.sub.2, Al.sub.2O.sub.3, Ta.sub.2O.sub.5, LaO.sub.2, NbO.sub.2, LiNbO.sub.3, BaSrTiO.sub.3, SrTiO.sub.3, ZrO.sub.2, SrZrO.sub.3, Nb-doped SrTiO.sub.3, Cr-doped SrTiO.sub.3, and Cr-doped SrZrO.sub.3.
(19) In general, it has been very difficult to actually apply the P-type metal oxide semiconductor to an element due to an extremely low current density. To solve such difficulty, the P-type metal oxide semiconductor layer may have a band gap of 3 eV or less, for example, 2 eV or less. In this case, the current density of the P-type metal oxide semiconductor layer may be significantly improved. Alternatively, the P-type metal oxide semiconductor layer may have a band gap of 1 eV or more. As an example, the P-type metal oxide semiconductor layer which satisfies this condition may be CuO.sub.x (1.1<x≤1.5, a band gap is in a range of 1.2 eV to 1.4 eV) or CoO.sub.x (1.1<x≤1.5, a band gap is in a range of 1.4 eV to 1.6 eV). Further, the P-type metal oxide semiconductor layer may have an atomic ratio of oxygen in a range 10% to 50%, specifically, 30% to 50%, greater than a case in which an atomic ratio of oxygen with respect to a metal satisfies a stoichiometric ratio. Further, the P-type metal oxide semiconductor layer which satisfies this condition may be CuO.sub.x (1.1<x≤1.5) or CoO.sub.x (1.1<x≤1.5).
(20) The first electrode 100 and the second electrode 300 may be formed of materials which may achieve an ohmic contact with the first conductivity type metal oxide semiconductor layers 210 and 230 connected thereto, respectively. As an example, the first electrode 100 and the second electrode 300 each may be Al, W, Pt, Ti, TiN, TaN, WN, or Cu.
(21) Further, a method of manufacturing a two-terminal switching element according to an embodiment of the present invention will be described with reference to
(22) The method of manufacturing the two-terminal switching element according to an embodiment of the present invention may include forming a first conductivity type lower metal oxide semiconductor layer 210 on a first electrode 100, forming a second conductivity type metal oxide semiconductor layer 220 on the first conductivity type lower metal oxide semiconductor layer 210, forming a first conductivity type upper metal oxide semiconductor layer 230 on the second conductivity type metal oxide semiconductor layer 220, and forming a second electrode 300 on the first conductivity type upper metal oxide semiconductor layer 230.
(23) Referring to
(24) As the first conductivity type and the second conductivity type are opposite conductivity types, one may be a P-type and the other may be an N-type. Therefore, the two-terminal switching element may have a structure of P-N-P or N-P-N.
(25) The first electrode 100, the lower metal oxide semiconductor layer 210 having the first conductivity type, the second conductivity type metal oxide semiconductor layer 220, the upper metal oxide semiconductor layer 230 having the first conductivity type, and the second electrode 300 may be formed using a sputtering method with an appropriate target. Specifically, when the P-type metal oxide semiconductor layer among the metal oxide semiconductor layers 210, 220, and 230 is formed, the sputtering method may be performed in an atmosphere in which inert gas and oxygen are mixed. As a result, a metal vacancy is formed in the P-type metal oxide semiconductor layer, and thus a current density of the P-type metal oxide semiconductor layer may be improved. However, the metal vacancy is not limited thereto, and may also be formed using a pulsed laser deposition (PLD) method, a thermal evaporation method, an electron-beam evaporation method, a physical vapor deposition (PVD) method, a molecular beam epitaxy (MBE) deposition method, or a chemical vapor deposition (CVD) method.
(26) After the second electrode 300 is formed, annealing such as heat treatment, ultraviolet (UV) treatment, or combination treatment in which a plurality thereof are applied may be performed. In this case, an on-current density and an on/off ratio of the two-terminal selective element may be improved, and a threshold voltage (a turn-on voltage) may be lowered. The heat treatment may be heat treatment using rapid thermal annealing (RTA) or a furnace. The UV treatment may be annealing using a UV lamp and may be performed using UV-C (UV having a wavelength in a range of 100 nm to 280 nm).
(27)
(28) Referring to
(29) At least after the switching layer 200 is formed, for example, before the intermediate electrode 400 is formed after the switching layer 200 is formed, or before the variable resistive layer 500 is formed after the switching layer 200 and the intermediate electrode 400 are formed thereon, annealing may be performed. The annealing may be heat treatment, UV treatment, or combination treatment in which a plurality thereof are applied. In this case, an on-current density and an on/off ratio of the two-terminal selective element SD may be improved, and a threshold voltage may be lowered. The heat treatment may be heat treatment using RTA or a furnace. The UV treatment may be annealing using a UV lamp and may be performed using UV-C (UV having a wavelength in a range of 100 nm to 280 nm).
(30) Each of the end electrodes 150 and 350 and the intermediate electrode 400 may be an Al, W, Pt, Ti, TiN, TaN, WN, or Cu layer. However, the end electrodes provided at both sides of the switching layer 200 and the immediate electrode may be formed with the same material layer. In this case, the symmetry of the switching element SD may be improved. However, this is not limited thereto.
(31) The switching layer 200 includes a pair of the first conductivity type metal oxide semiconductor layers 210 and 230 and a second conductivity type metal oxide semiconductor layer 220 disposed between the first conductivity type metal oxide semiconductor layers 210 and 230. One of the first conductivity type metal oxide semiconductor layers 210 and 230 may be electrically connected to one of the end electrodes 150 and 350. The first conductivity type metal oxide semiconductor layers 210 and 230 may be a lower metal oxide semiconductor layer 210 having a first conductivity type and an upper metal oxide semiconductor layer 230 having a first conductivity type. As an example, the lower metal oxide semiconductor layer 210 is connected to the first end electrode 150. When the intermediate electrode 400 is disposed, the upper metal oxide semiconductor layer 230 may be connected to the intermediate electrode 400. The first conductivity type metal oxide semiconductor layers 210 and 230 and the second conductivity type metal oxide semiconductor layer 220 will be described in detail with reference to the embodiment described with reference to
(32) The variable resistive layer 500 may be electrically connected to the upper metal oxide semiconductor layer 230. When the intermediate electrode 400 is disposed, the variable resistive layer 500 is connected to the intermediate electrode 400. The variable resistive layer 500 may be a bipolar variable resistive layer. The variable resistive element RM including the variable resistive layer 500 may include a magnetoresistive random access memory (MRAM), specifically a spin transfer torque MRAM. In this case, the variable resistive layer 500 has a magnetic tunnel junction (MTJ) structure, and the MTJ structure may have a ferromagnetic pinned layer 510, a tunnel barrier layer 520, and a ferromagnetic free layer 530, which are sequentially stacked. The MTJ structure may further include a pinning layer (nor shown) under the ferromagnetic pinned layer 510. The ferromagnetic pinned layer 510, which is a layer in which magnetization reversal does not occur, may be a CoFeB layer or a FePt layer. The tunnel barrier layer 520 may be an aluminum oxide layer or a magnesium oxide layer. The ferromagnetic free layer 530, which is a layer in which magnetization reversal occurs at a critical current density or more, may be a CoFeB layer or a FePt layer. The ferromagnetic free layer 530 may have a magnetization direction opposite that of the pinned layer at a positive critical current density or more, and at a negative critical current density or less. Therefore, the spin transfer torque MRAM may operate as a bipolar element.
(33) Further, a method of manufacturing a resistive memory cross-point array according to an embodiment of the present invention will be described with reference to
(34) The method of manufacturing the resistive memory cross-point array according to an embodiment of the present invention may include forming a switching layer 200 including a first conductivity type lower metal oxide semiconductor layer 210, a second conductivity type metal oxide semiconductor layer 220, and a first conductivity type upper metal oxide semiconductor layer 230 on a first end electrode 150, forming a second end electrode 350 on the switching layer 200, and forming a variable resistive layer 500 on the first end electrode 150 before the switching layer 200 is formed or on the switching layer 200 before the second end electrode 350 is formed.
(35) Referring to
(36) An intermediate electrode 400 may be formed between the switching layer 200 and the variable resistive layer 500. In this case, the first end electrode 150, the switching layer 200, and the intermediate electrode 400 may constitute a two-terminal switching element SD, and the intermediate electrode 400, the variable resistive layer 500, and the second end electrode 350 may constitute a variable resistive element RM. Furthermore, the first end electrode 150 may serve as a word line and an additional word line may be connected to the first end electrode 150. Further, the second end electrode 350 may serve as a bit line and an additional bit line may be connected to the second end electrode 350.
(37) At least after the switching layer 200 is formed, for example, before the intermediate electrode 400 is formed after the switching layer 200 is formed, or before the variable resistive layer 500 is formed after the switching layer 200 and the intermediate electrode 400 are formed thereon, annealing may be performed. The annealing may be heat treatment, UV treatment, or combination treatment in which a plurality thereof are applied. In this case, an on-current density and an on/off ratio of the two-terminal selective element SD may be improved, and a threshold voltage (a turn-on voltage) may be lowered. The heat treatment may be heat treatment using RTA or a furnace. The UV treatment may be annealing using a UV lamp and may be performed using UV-C (UV having a wavelength in a range of 100 nm to 280 nm).
(38)
(39) Referring to
(40) In one embodiment, when a set voltage is applied to the variable resistive element RM, oxygen ions included in the RRAM layer 600 may move to the second end electrode 350 to be stored in the second end electrode 350. In this case, the number of oxygen vacancies is increased in the RRAM layer 600 and the RRAM layer 600 may be changed to have low resistance. Further, when a reset voltage is applied to the variable resistive element RM, the oxygen ions which were moved to the second end electrode 350 may return to the RRAM layer 600. In this case, the number of oxygen vacancies is reduced in the RRAM layer 600 and the RRAM layer 600 may be changed to have high resistance. To this end, the second end electrode 350 may be TiN or WN in which resistance is hardly changed even after the storing of the oxygen. In this case, each of the first end electrode 150 and the intermediate electrode 400 may be an Al, W, Pt, Ti, TaN, WN, or Cu layer.
(41)
(42) Referring to
(43) A ½V.sub.write is applied to a bit line B.sub.m+1 selected from the bit lines and a ground voltage is applied to bit lines B.sub.m, B.sub.m+2, and B.sub.m+3 not selected from the bit lines. A −½V.sub.write is applied to a word line W.sub.n+1 selected from the word lines W.sub.n, W.sub.n+1, W.sub.n+2, and W.sub.n+3 and a ground voltage is applied to word lines W.sub.n, W.sub.n+2, W.sub.n+3 not selected from the word lines. A V.sub.write may be applied to a selected unit cell A located at a point at which the selected bit line B.sub.m+1 and the selected word line W.sub.n+1 cross, and 0 V, ½V.sub.write, or −½V.sub.write may be applied to the remaining non-selected unit cells.
(44) The V.sub.write may have a value of a threshold voltage of the two-terminal switching element SD or more and a value of a set voltage of the variable resistive element RM or more, and the ½V.sub.write may have a value less than the set voltage of the resistive memory element RM. Therefore, in the selected unit cell, only the resistive memory element RM may be selectively changed in a low resistive state (LRS). Meanwhile, in the non-selected unit cell, the state of the resistive memory element RM may not be changed, and the previous state thereof may be maintained.
(45)
(46) Referring to
(47) The −V.sub.write may have a value of a backward threshold voltage of the two-terminal switching element SD or less and a reset voltage or less of the resistive memory element RM. Therefore, in the selected unit cell, only the resistive memory element RM may be selectively changed in a high resistive state (HRS). Meanwhile, in the non-selected unit cell, the state of the resistive memory element RM may not be changed, and a previous state thereof may be maintained.
(48) Hereinafter, exemplary experimental examples will be introduced to help with understanding of the present invention. However, the experimental examples below are intended only to help with understanding of the present invention, and the present invention is not limited thereto.
Experimental Examples; Examples
Manufacturing Example 1: Manufacturing of P-N-P Switching Element, IGZO_5 nm
(49) A 30 nm Ti layer was formed on a SiO.sub.2 layer of a Si substrate including a 200 nm layer of the SiO.sub.2 using a magnetron sputtering method with a Ti target in a pure argon atmosphere, and then 100 nm of a Pt layer was formed using a magnetron sputtering method with a Pt target in the same atmosphere. Then, a P-type metal oxide semiconductor layer, which was a 30 nm CoO.sub.x layer, was formed on the Pt layer using a magnetron sputtering method with a CoO target in an atmosphere in which 1.1 sccm of oxygen and 10 sccm of argon were mixed. An N-type metal oxide semiconductor layer, which was a 5 nm IGZO layer, was formed on the CoO.sub.x layer using a magnetron sputtering method with an IGZO (InGaZnO) target in a pure argon atmosphere. A P-type metal oxide semiconductor layer, which was a 30 nm CoO.sub.x layer, was formed on the IGZO layer using a magnetron sputtering method with a CoO target in an atmosphere in which 1.1 sccm of oxygen and 10 sccm of argon were mixed. Then, a 100 nm Pt pattern was formed on the CoO.sub.x layer using a magnetron sputtering method with a Pt target and using a metal shadow mask in a pure argon atmosphere. Then, UV treatment in which ultraviolet in a UV-C (UV having a wavelength in a range of 100 nm to 280 nm) region was emitted for 20 minutes or more was performed in a high vacuum state of 10.sup.−6 Torr or less.
Manufacturing Example 2: Manufacturing of P-N-P Switching Element, IGZO 10 nm
(50) A switching element was manufactured using the same method as Manufacturing Example 1 of the switching element except that a 10 nm IGZO layer was formed.
Manufacturing Example 3: Manufacturing of P-N-P Switching Element, IGZO 20 nm
(51) A switching element was manufactured using the same method as Manufacturing Example 1 of the switching element except that a 20 nm IGZO layer was formed.
Manufacturing Example 4: Manufacturing of P-N-P Switching Element, IGZO 50 nm
(52) A switching element was manufactured using the same method as Manufacturing Example 1 of the switching element except that a 50 nm IGZO layer was formed.
Manufacturing Example 5: Manufacturing of P-N-P Switching Element, Except UV Treatment
(53) A switching element was manufactured using the same method as Manufacturing Example 1 except that UV treatment was not performed.
(54)
(55) Referring to
(56)
(57) Referring to
(58)
(59) Referring to
Manufacturing Example 6: Manufacturing of Variable Resistive Element
(60) A 30 nm Ti layer was formed on a SiO.sub.2 layer of a Si substrate including a 200 nm layer of the SiO.sub.2 using a magnetron sputtering method with a Ti target in a pure argon atmosphere and then a 100 nm Pt layer was formed using a magnetron sputtering method with a Pt target in the same atmosphere. Then, the RRAM layer, which was a 30 nm TiO.sub.x layer (x=1.75), was formed on the Pt layer using a magnetron sputtering method with a TiO.sub.2 target in an atmosphere in which 10 sccm of oxygen and 6 sccm of argon were mixed. A 100 nm TiN pattern was formed on the TiO.sub.x layer using a magnetron sputtering method with a Ti target and using a metal shadow mask in an atmosphere in which 1.5 sccm of nitrogen and 8 sccm of argon were mixed.
(61)
(62) Referring to
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(64) Referring to
(65) Although the invention has been described in detail with reference to exemplary embodiments, the invention is not limited thereto. Those skilled in the art may make various modifications and changes without departing from the spirit and scope of the present invention.