DUAL ELECTRON INJECTOR STRUCTURE AND SEMICONDUCTOR MEMORY DEVICE INCLUDING A DUAL ELECTRON INJECTOR STRUCTURE

Abstract: A DEIS (Dual Electron Injector Structure) EAROM (Elec­ trically Alterable Read Only Memory) device has a silicon-­ rich, silicon dioxide region 5 between the dual injector regions (1,3). The region (5) has an excess of silicon therein which is less than the excess of silicon in the injector re­ gions (1,3). The device differs from known DEIS EAROM devices in that the insulator layer between the injectors is rendered conductive to a desired degree by causing a com­ pound insulator like SiO₂ to be off-stoichiometry during de­ position so that the resulting insulator becomes silicon rich. Alternatively, the insulator may be deposited together with material which renders the insulator conductive or a metal­ lic specie may be added to the insulator by diffusion or ion implantation after the insulator is formed. The resulting slightly conductive insulator provides a means for draining off trapped charge in the insulator resulting in a device of such improved cyclibility that the DEIS EAROM can be used as a Non-Volatile Random Access Memory (NVRAM) ca­ pable of from 10⁸ to greater than 10¹⁰ cycles before threshold collapse occurs. The conductive insulator is designed so that it is con­ ductive only at high electric fields encountered during writ­ ing and erasing and highly blocking at low fields encoun­ tered during reading or storage operations.

Description: DUAL ELECTRON INJECTOR STRUCTURE AND SEMICONDUCTOR MEMORY DEVICE INCLUDING A DUAL ELECTRON INJECTOR STRUCTURE This invention relates to a dual electron injector structure for a non-volatile semiconductor memory device and to a semiconductor memory device including a dual electron injector structure. In published European Patent Application 16246 there is described a graded or stepped silicon concentration structure for making a charge storage device wherein injection of holes or electrons from one contact is possible without compensating injection of electrons or holes from the other contact. This is achieved by the inclusion of a charge trapping layer in the thick insulator region adjacent to the silicon semiconducting body. The trapping layer is situated at a distance of approximately 50 or more from the Si-insulator interface to prevent trapped carriers from tunnelling from this layer to the Si substrate. This trapping layer captures and stores either electrons (write operation) or holes (erase operation) with as close to 100% efficiency as possible. An electrically-alterable read-only- memory (EAROM) device using a metal-insulator-semiconductor structures is also described. The structure is fabricated by forming several pyrolytic or CVD SiO2 layers over a relatively thick thermal SiO2 with the pyrolytic SiO layers having sequentially increasing excess Si content. The 2 trapping layer is formed by controlled impurity ion-implantation or by diffusion of the impurity into the relatively thick thermal SiO2 layer, or by deposition of the impurity on thermal SiO with stoichiometric CVD 2 SiO2 isolating it from the injector region consisting of the Si-rich CVD SiO2 layers. This structure has the limitation of being only a good single carrier electron injector since few holes are injected for the opposite polarity. Consequently, when used in memory devices "erase" times are long (minutes) as compared to write times (milliseconds). See for example the publications to D. J. DiMaria, entitled "Graded or Stepped Energy Band-Gap Insulator MIS Structures (GI-MIS for SI-MIS)" J. Appl. Phys., 50, 5826 1979 and to D. J. DiMaria et al, entitled "High Current Injection into SlO2 From Si-Rich SiO2 Films and Experimental Applications", J. Appl. Phys. 51, (5) May 1980, pp. 2722-2735. An improvement on single electron injector structures is described in published European Patent Application 34653. The improvement is the addition of a vertically positioned second injector proximate to a trapping layer or floating gate structure in the insulator layer. The dual injector structure so provided can effectively inject holes at the opposite polarity as easily as the injection of electrons by actually ejecting the trapped electrons using the added bottom injector with these being collected by the top gate contact. Thus, when used in a memory device, it provides erase times equivalent to the write times obtained in the single injector memory device An example of a structure employing the dual injector is an MGOS FET to perform a memory function. More specifically, the MGOS structure employs a charge trapping layer or floating gate near the Si-SiO2 interface of the gate structure in an FET configuration. Layers of Si-rich SiO2-SiO2-Si-rich SiO2 are provided between the control gate and trapping layer or floating gate of the memory device. This insulator stack is referred to as a Dual Electron Injector Structure (DEIS). Writing or erasing is performed by applying a negative and positive voltage, respectively, to the control gate which injects electrons from the top and bottom injector to the floating gate or back to the control gate. The background operation, fabrication and characteristics of the above described device are discussed in detail in an article entitled, "Electrically-alterable read-only-memory using Si-rich SiO2 injectors and a floating polycrystalline silicon storage layer" by D.J. DiMaria et al, J. Appl. Phys. 52 t7), July 1981, 4825-4842. In this article, attention is particularly directed to the fact that the DEIS (Dual Electron Injector Structure) EAROM experiences a phenomenon called threshold collapse after a device has been subjected to writing and erasing functions between 10 and 106 cycles. This is due to electronic charge trapping in the SiO2 insulator disposed between the Si-rich SiO2 layers. To the extent that the prior art device experiences threshold collapse at between 10 and 106 cycles, the DEIS EAROM cannot be extended to a pure Non-Volatile Random-Access-Memory (NVRAM). The present invention provides a dual electron injector structure comprising first, second and third regions, the first region being disposed on top of the second region and the second region on top of the third region, the first and third regions consisting of a mixture of insulating and conductive materials, the structure being characterised in that the second region consists of a mixture of insulating and conductive materials and in that the second region has a higher resistance than that of the first and second layers. This invention can lead to the production of a pure Non-Volatile Random-Access-Memory (NVRAM) device which is not subject to threshold collapse for more than 106 cycles. How the invention can be carried out will now be described by way of example, with reference to the accompanying drawings, in which: FIG. 1 represents a non-volatile n-channel FET memory device including a dual electron injector structure according to the invention; FIG. 2 is a graph showing the variations in threshold voltage with the number of write and erase cycles for three different values of resistivity of the conductive insulator disposed between injectors; ; FIG. 3 is a graph similar to that shown in FIG. 2 which shows that, for high values of R (where R is the ratio of N20 to SiH4 in the gas 0 0 phase in the CVD reactor) representing pure SiO2, total threshold collapse occurs before 10 cycles, while, for lower values of R 0 threshold collapse -does not occur for cycles in excess of 107; and FIG. 4 is a graph of threshold voltage variation with time (secs) for insulators having R values of 30, 40, 50 and 200. 0 Referring to FIG. I, a dual electron injector structure of a non volatile, n-channel, FET memory device is comprises a Si-rich SiO2 region 1 which is contiguous with and beneath a polysilicon or metal gate region 2, and a second Si-rich S02 region 3 contiguous with and atop a floating gate region 4 which may be made of polysilicon or metal. Regions 1,3 are separated by means of an SiO2 region 5 which has been rendered slightly conductive by the addition of 1-6% Si to drain off trapped charge in this region. The eintervening Si02 region 5 is con- ductive at the high electric fields used for writing and erasing the device and highly blocking to the motion of charge between gates at low electric fields used for reading or storage. As a result, the ability to cycle the device of FIG. 1 between written and erased states is 8 improved to greater than 10 cycles. Si-rich SiO2 area 5 is provided by the chemical vapour deposition of SiO2 which is off stoichiometry to the extent it contains about 1-6% excess atomic Si. Si-rich SiO2 regions 1,3 have graded or stepped concentrations of Si which are prepared by the chemical vapour deposition of a plurality of SiO2 layers having varying concentrations of Si. The enumber of layers, the thickness of each layer, and the concentration of excess Si in each successive layer making up regions 1,3 is a matter of design choice. Increasing the Si content of the Si-rich SiO2 regions 1,3 enhances the electron injection capability, thereby decreasing write and/or erase voltages and/or times. A preferred Si content of regions 1,3 is from about 46 to about 60 atomic per cent Si. The operation of the injectors is not very sensitive to injector thickness (from 100A to lOOOA) or the exact Si content to within a few percent because the interfaces of the lower resistance Si-rich SlO2 layers 1,3 with the higher resistance layer 5 control the electron injection phenomenon. In FIG. 1, first and second n regions 6,7, respectively are shown formed in a p- silicon substrate 8. voltages Vs, VD and V , otherwise 5 g identified in FIG. 1 by the captions SOURCE, DRAIN and GATE, respectively, are connected via metallization 9,10 and 11, respectively, to n + region 6, n region 7 and polysilicon gate 2. The FET structure shown in FIG. 1 may be fabricated using a selfaligned, double poly-Si process. After defining thick field oxide regions (not shown), the exposed substrate portion of the device of FIG. 1 is subjected to a thermal oxidation step which forms a layer of Sio, in the thickness range from 50-1000 on the surface of the substrate. The latter is a 0.5?cm (100), p-type, single crystal silicon substrate. Next, a 2000 thick polysilicon layer is deposited and doped n-degenerate with POCK3 in a well known manner to form the floating charge storage layer 4 of FIG. 1. The injector stack comprised of layers 3,5,1 of FIG. 1 consists of Chemically Vapour Deposited (CVD) silicon-rich silicon dioxide layers wherein layer 5 is silicon rich to a lesser extent than the layers 3,1 of FIG. 1. The silicon richness of the layers is controlled during deposition by controlling the gaseous concentration ratio of N20 to SiH4 in the CVD reactor. Thus, where the ratio is 100 for deposition of a layer of pure SiO2, it is reduced to 50 to provide an SiO2 layer which has a 1-3% excess of silicon in it. Thus, where stoichiometric SiO2 has approximately 33 atomic % Si in it, the Si-rich SiO2 having an excess of 1-3 atomic % Si in it would now contain 34-36 atomic percent Si. In a preferred embodiment, injectors 1,3 may be deposited by chemical vapour deposition in a range of thicknesses of l00A-200A and contain excess silicon in a range of 1-13 atomic percent. Layer 5 may O O be deposited in a thickness range of l50A-600A and contain excess silicon in a range of 1-6 atomic percent. After deposition of injector 1, a 2000A thick polysilicon, ndegenerate layer similar to layer 4 is deposited and doped. In a succeeding step, plasma etching, reactive ion etching and wet etching are used to define source and drain. Source and drain are then diffused in a well known way and a 1000 thick oxide is regrown at 1000 C over the source and drain. A protective 3000A layer of CVD SiO2 followed by a phosphosilicate glass (PSG) passivation are deposited and annealed at 10000C. Finally, contact holes to the source drain and polysilicon gate 2 are defined and etched, followed by palladium silicide (Pd2Si) and aluminum metallizations and a 4000C anneal for 20 minutes in forming gas (90% N2-10% H2). CVD silicon-rich silicon dioxide layers 1,3 are deposited at 700 C using a ratio of concentrations of N2O to SiH4 in the gas phase of 3 and, under such conditions, contain 46% atomic silicon or 13% excess silicon over that found in pure SiO2. From the foregoing, it should be clear that by simply adjusting the above mentioned ratio, the amount of silicon richness can be easily controlled. An exemplary device fabricated using the above outlined process has a channel length of 2.5 x 10-4 SiO2.cm after photolithography, but effectively is about 1.8 x 10-4 cm after diffusion drive in and subsequent high temperature processing. The channel width is 4.0 x 10-4 cm and the FET channel area 7.2 x 10-8 The actual injecting area for writing and erasing can be smaller, for example, 2.5 x 10 cm x 2 x 10 cm = 5x10-8 cmê. The FET DEIS structure of FIG. 1 is placed in the write or erase modes by using moderate gate voltages between -5V and -40V and +5V and +40V, respectively, on the control gate electrode 11, the exact voltage magnitude depending on device configuration. Other device configurations with three or more parts which use only positive voltages for either the write or erase operations have been discussed in the article entitled "Dual-Electron-Inj ector-Structure Electrically Alterable Read-Only Memory Modeling Studies", by D. J. DiMaria et al, IEEE Transactions on Electron Devices, ED-28, pp. 1047-1053, 1981. Once floating gate 4 is charged positively or negatively, the device can be read with voltages between 0 to +5V on control gate 2 and a small voltage applied between the source and drain 7. If the structure is in the erased or written state, current or no current will flow, respectively, in the FET channel between source 6 and drain 7. This structure has good charge retention either grounded or floating (at least for periods of one day at 250C) as shown in FIG. 4, and thus serves as a non-volatile memory. It can be cycled approximately 106 to 108 times as opposed to prior art arrangements which could be cycled 103 to 105 times. As with the prior art, the threshold voltage window collapse is ultimately caused by trapped charge buildup in the CVD Si enriched SiO2 region 5. Referring now to FIG. 2 there is shown therein the variation in threshold voltage with the number of write and erase cycles for three different values of resistivity (R =50 being indicative of the most 0 resistive intervening off-stoichiometry Sio, layer) of the layer 5 disposed between injectors or layers 1,3. To obtain this data devices similar to that described hereinabove were utilized except that the region 5 was formed with different amounts of excess silicon. The region 5 in all instances was 600 thick while the resistivity values were 30,40 and 50 signifying approximately 5-6 excess silicon, approximately 3-4% excess silicon and approximately 1-2% excess silicon, respectively. It should be noted that the onset of threshold collapse which is due to the storing of trapped charge in the region 5 does not begin until after at least 106 cycles. Writing is performed by applying a negative voltage V g to control gate 2 which injects electrons from the silicon-rich silicon dioxide injector layer 1 into the intervening oxide layer 5 which then flow in the electric field to the floating polysilicon gate 4. Erasing is performed by applying a positive voltage V g to control gate 2 which injects electrons from the bottom siliconrich silicon dioxide injector 3 back to control gate 2. The negative and positive voltages shown with the curves are those utilized for writing and erasing, respectively In all instances, the voltages were applied for 500 microseconds. The introduction of silicon to render the normally insulating layer 5 slightly conductive does not prevent ultimate threshold voltage collapse. This expedient, however, does extend the ability to cycle beyond 1010 cycles before complete threshold voltage collapse occurs. One explanation is that the probability of capture of electrons in layer 5 becomes more and more likely as the device is cycled between its write and erase function. FIG. 3 is a graph similar to that shown in FIG. 2 which shows that for a high value of R equal to 200 which represents pure silicon 0 6 dioxide, total threshold collapse occurs before 10 cycles while for a lower value of R equal to 30, threshold collapse does not occur until 0 after 10 cycles. FIG. 4 is a graph of threshold voltage variation with time for devices with regions 5 of FIG. 1 having R values of 30, 40, 50, and 0 200. This graph shows that for relatively high values of resistivity (for example, R equal to 50), electron leakage from a floating gate to a control gate is approximately the same as the leakage for a pure SiO2 insulator (R =200). 0 The use of a slightly conductive region between silicon-rich silicon dioxide injectors enhances the ability to cycle a device between its write and erase modes. To the extent that lower writing and erasing voltages result from the use of a slightly conductive region, power dissipation in such devices is decreased. In addition, the voltages utilized to write and erase become approximately the same value. While the above improvements come about as a result of adding more silicon to the silicon dioxide insulator, it should be appreciated that retention of charge is only slightly degraded. The distribution of the conductive material in regions 1,3,5 is not critical. The conductive material may be uniformly or nonuniformly distributed in these regions. Each region may be formed of a plurality of layers each having a different concentration of conductive material so that the concentration is graded from one interface to another interface. Also, it should be appreciated that, while there has just been described an application of the invention to an n-channel FET, the invention may also be applied to p-channel FET's. While the materials silicon and silicon dioxide are the preferred materials, it should be appreciated that other insulating materials such as aluminum oxide and silicon nitride and practically any metal or semimetal including silver, gold, tantalum, silicon and aluminum metals, may also be utilized in the practice of the present invention. The insulator may be deposited together with metal which renders the insulator conductive or a metallic species may be added to the insulator by diffusion or ion implantation after the insulator is formed. The slightly conductive insulator is designed so that it is conductive only at high electric fields encountered during writing and erasing and highly blocking at low fields encountered during reading or storage operations. Obviously, insulating materials and metals which are compatible with each other and with semiconductor processing techniques will find wider use than other material combinations which do not lend themselves so readily to semiconductor processing.

Claims: CLAIMS 1. A dual electron injector structure comprising first, second and third regions (1,5,3), the first region (1) being disposed on top of the second region (5) and the second region (5) on top of the third region (3), the first and third regions (1,3) consisting of a mixture of insulating and conductive materials, the structure being characterised in that the second region (5) consists of a mixture of insulating and conductive materials and in that the second region (5) has a higher resistance than that of the first and second layers. 2. A structure as claimed in claim 1, in which the conductive material in the first, second and third regions is metallic material. 3. A structure as claimed in claim 1, in which the conductive material comprised in the first, second and third regions is semimetallic material. 4. A structure as claimed in claim 3, in which the conductive material in the first, second and third regions is silicon. 5. A structure as claimed in claim 4, in which the insulating material in the first, second and third regions is silicon dioxide and the first and third regions contain up to 25% excess silicon over that found in stoichiometric silicon dioxide and wherein the second region contains up to 6% excess silicon over that found in the stoichiometric silicon dioxide. 6. A structure as claimed in any preceding claim, in which there is a uniform distribution of the conductive material in each of the first, second and third regions. 7. A structure as claimed in any of claims 1 to 5, in which there is a non-uniform distribution of the conductive material in each of the first, second and third regions. 8. A structure as claimed in any of claims 1 to 4, 6 and 7, in which the insulating material in the first, second and third regions is silicon dioxide, silicon nitride or aluminium oxide. 9. A structure as claimed in any preceding claim, further including first and second conductors contiguous with said first and third regions respectively. 10. A semiconductor memory device comprising a semiconductor substrate (8) of one conductivity type having a pair of regions (6,7) of opposite conductivity type disposed therein and forming a channel region therebetween; an insulating layer (12) formed over said channel region, a floating gate electrode (4) formed over said insulating layer (12); a dual electron injector structure (1,5,3) formed over said floating gate electrode (4), and a gate electrode (2) disposed over said dual electron injector structure, characterised in that the dual electron injector structure is as claimed in any preceding claim.

Inventors: DIMARIA, DONELLI JOSEPH, DONG, DAVID WAH
Applicants: INTERNATIONAL BUSINESS MACHINES CORPORATION
Application year: 1982
Main classification: G11C11
IPC codes: H01L21, H01L29, H01L27