公开(公告)号：US3929589A

公开(公告)日：1975-12-30

申请号：US44065774

申请日：1974-02-08

Applicant: BELL TELEPHONE LABOR INC

Inventor： ERMANIS FELIX ,  SCHWARTZ BERTRAM

IPC: C25D5/02 ,  C25D11/32 ,  H01L21/00 ,  H01L21/3063 ,  H01L21/316 ,  H01L29/00 ,  C23B11/02

CPC classification number: H01L21/00 ,  C25D5/02 ,  C25D11/32 ,  H01L21/30635 ,  H01L21/31654 ,  H01L29/00

Abstract: A method for selectively oxidizing the surface of a III-V compound semiconductor wafer. A photoresist mask is first formed on the surface of the semiconductor leaving exposed the areas to be oxidized. The semiconductor is then made the anode in an electrolytic cell wherein the electrolyte comprises water and a source of ions for adjusting the pH or providing conductivity to the solution. In a preferred embodiment, the wafer is a gallium containing compound semiconductor and in particular GaAs, and the electrolyte is water and an ammonium acid phosphate. The oxide is grown electrolytically only into the exposed areas of the wafer, and the photoresist may then be stripped off leaving the desired oxide pattern.

Abstract translation: 一种用于选择性氧化III-V族化合物半导体晶片表面的方法。 首先在半导体的表面上形成光致抗蚀剂掩模，从而暴露待氧化的区域。 然后将半导体制成电解池中的阳极，其中电解质包含水和用于调节pH或为溶液提供导电性的离子源。 在优选实施例中，晶片是含镓化合物半导体，特别是GaAs，电解质是水和磷酸铵。 氧化物仅电解生长到晶片的暴露区域中，然后可以剥离光致抗蚀剂，留下所需的氧化物图案。

公开(公告)号：US3882000A

公开(公告)日：1975-05-06

申请号：US46842374

申请日：1974-05-09

Applicant: BELL TELEPHONE LABOR INC

Inventor： SCHWARTZ BERTRAM ,  SPITZER STUART MARSHALL ,  WEIGLE GREGORY DYETT

IPC: C25D11/32 ,  H01L21/316 ,  C23F17/00 ,  H01L7/18

CPC classification number: C25D11/32 ,  H01L21/31687

Abstract: A method of forming a composite oxide on III-V compound semiconductors is disclosed. An oxidizable metal such as Al, Ni, Ta, Ti, Zn or alloys including said metals is deposited on the surface of the semiconductor or on a native oxide grown on the semiconductor. The structure is subjected to an electrolytic oxidation so that all the metal is oxidized and a native oxide is grown into the surface resulting in a composite oxide comprising the native oxide and the metal oxide. This composite oxide can serve to passivate the semiconductor as well as provide a stable mask for etching and diffusion processes. In addition, the composite oxide appears to have a high dielectric strength for use in MOS devices.

Abstract translation: 公开了在III-V族化合物半导体上形成复合氧化物的方法。 可氧化金属如Al，Ni，Ta，Ti，Zn或包含所述金属的合金沉积在半导体的表面上或在半导体上生长的天然氧化物上。 对该结构进行电解氧化，使得所有的金属被氧化，并且将天然氧化物生长到表面中，产生包含天然氧化物和金属氧化物的复合氧化物。 该复合氧化物可用于钝化半导体，并为蚀刻和扩散工艺提供稳定的掩模。 此外，复合氧化物似乎具有用于MOS器件的高介电强度。

公开(公告)号：US3585075A

公开(公告)日：1971-06-15

申请号：US3585075D

申请日：1969-02-26

Applicant: BELL TELEPHONE LABOR INC

Inventor： IRVIN JOHN C ,  SCHWARTZ BERTRAM

IPC: H01L21/285 ,  H01L29/00 ,  H01L29/47 ,  B44D1/18

CPC classification number: H01L29/475 ,  H01L21/28581 ,  H01L29/00

Abstract: A LOW WORK FUNCTION SCHOTTKY BARRIER DIODE IS OBTAINED BY COATING A CONTACT REGION UPON A GALLIUM ARSENIDE SUBSTRATE WITH A TIN HALIDE FLUX AND SUBSEQUENTLY DEPOSITING TIN THEREON.

公开(公告)号：US3898141A

公开(公告)日：1975-08-05

申请号：US44065674

申请日：1974-02-08

Applicant: BELL TELEPHONE LABOR INC

Inventor： ERMANIS FELIX ,  SCHWARTZ BERTRAM

IPC: H01L21/3063 ,  H01L21/316 ,  B23P1/00

CPC classification number: H01L21/02241 ,  H01L21/02258 ,  H01L21/30635 ,  H01L21/31679

Abstract: A method for oxidation and etching of a III-V compound semiconductor in a single solution. The semiconductor is made the anode in an electrolytic cell wherein the electrolyte is water raised to a pH of 8 or above by a source of hydroxyl ions such as NH4OH. When an appropriate electric field is established in the cell, an oxide is grown into the surface of the semiconductor. Then the field is lowered or turned off and the oxide dissolves faster than it is grown resulting in an etching of the semiconductor material previously consumed in forming the oxide. The method permits electrochemical thinning of a semiconductor layer for such uses as FETS and IMPATTS and further allows formation of passivating layers on etched surfaces in situ.

Abstract translation: 在单一溶液中氧化和蚀刻III-V化合物半导体的方法。 将半导体制成电解池中的阳极，其中电解质是通过羟基离子源如NH 4 OH将水升至pH8或更高的pH。 当在电池中建立适当的电场时，氧化物生长到半导体的表面中。 然后场被降低或关闭，并且氧化物比其生长更快地溶解，导致先前在形成氧化物中消耗的半导体材料的蚀刻。 该方法允许半导体层的电化学稀化用于诸如FETS和IMPATTS的用途，并且还允许在蚀刻表面上原位形成钝化层。

公开(公告)号：US3890169A

公开(公告)日：1975-06-17

申请号：US34470273

申请日：1973-03-26

Applicant: BELL TELEPHONE LABOR INC

Inventor： SCHWARTZ BERTRAM ,  SPITZER STUART MARSHALL ,  WEIGLE GREGORY DYETT

IPC: H01L21/324 ,  H01L21/316

CPC classification number: H01L21/31654 ,  Y10S148/056 ,  Y10S148/065 ,  Y10S148/118 ,  Y10S252/951

Abstract: A method of forming a highly stable oxide on gallium arsenide containing compound semiconductors. A native oxide is grown on the surface of the semiconductor and dried during a suitable baking cycle. The oxide is then annealed at a temperature which is significantly higher than that of the baking cycle. This annealing step densifies the oxide and renders it particularly stable and impervious to impurities. In a particular embodiment, a diffusion mask is formed in accordance with the invention to permit selective area diffusion of impurities into a gallium arsenide containing compound semiconductor.

Abstract translation: 在含有砷化镓的化合物半导体上形成高度稳定的氧化物的方法。 在半导体的表面上生长天然氧化物，并在合适的烘烤循环期间干燥。 然后将氧化物在显着高于烘烤循环的温度下退火。 该退火步骤使氧化物致密化并使其特别稳定并且不渗透杂质。 在特定实施例中，根据本发明形成扩散掩模，以允许杂质选择性区域扩散到含砷化镓的化合物半导体中。

公开(公告)号：US3914465A

公开(公告)日：1975-10-21

申请号：US29212672

申请日：1972-09-25

Applicant: BELL TELEPHONE LABOR INC

Inventor： DYMENT JOHN CAMERON ,  SCHWARTZ BERTRAM

IPC: H01L21/306 ,  H01L21/316 ,  H01S5/028 ,  H01S3/18 ,  H01S3/19

CPC classification number: H01S5/028 ,  H01L21/30612 ,  H01L21/31654 ,  Y10S148/017 ,  Y10S148/056 ,  Y10S148/118

Abstract: A method for protecting the surface of GaAs junction lasers, in particular the cleaved mirror surfaces of such devices. A native oxide is first grown on the surface of the device by immersing the device in an aqueous H2O2 solution wherein the pH is 1.5-3.5. The device is then immersed in an aqueous H2O2 solution which has been adjusted to a pH of 6-8 by a suitable hydroxide. This double oxidation technique provides substantial protection against the deleterious effects of water on the mirror surfaces.

Abstract translation: 一种用于保护GaAs结激光器表面的方法，特别是这种器件的切割镜面。 首先通过将该装置浸入pH为1.5-3.5的H 2 O 2水溶液中，在该装置的表面上生长天然氧化物。 然后将该装置浸入H 2 O 2水溶液中，该水溶液通过合适的氢氧化物调节至pH为6-8。 这种双重氧化技术提供了大量的保护，防止水对镜面的有害影响。

公开(公告)号：US3865646A

公开(公告)日：1975-02-11

申请号：US42791573

申请日：1973-12-26

Applicant: BELL TELEPHONE LABOR INC

Inventor： LOGAN RALPH ANDRE ,  SCHWARTZ BERTRAM ,  TRACY JR JOSEPH CHARLES ,  WIEGMANN WILLIAM

IPC: G02B6/12 ,  G02B6/13 ,  H01L33/00 ,  H01S5/22 ,  H01L7/38 ,  H01L7/36

CPC classification number: G02B6/12 ,  G02B6/131 ,  H01L33/0062 ,  H01S5/22 ,  Y10S148/049 ,  Y10S148/051 ,  Y10S148/056 ,  Y10S148/065 ,  Y10S148/067 ,  Y10S148/072 ,  Y10S148/118 ,  Y10S148/145 ,  Y10S438/911 ,  Y10S438/945

Abstract: A method of fabricating dielectric optical waveguides comprises the steps of: (1) fabricating a single or double heterostructure from the GaAs-AlGaAs system preferably by liquid phase epitaxy or molecular beam epitaxy; (2) forming a native oxide layer on the top surface of the heterostructure by anodization in H2O2; (3) removing a portion of the oxide layer to form a mask and hence to define the waveguide shape in the direction of light propagation; and (4) forming a mesa-like structure with optically flat side walls by etching at a slow rate in Br2-CH3OH. After step (4) two alternative techniques leading to structurally different waveguides may be followed. In one technique, an AlGaAs layer is epitaxially grown over the mesa to form a two dimensional waveguide. In the other technique, the edges of the active region of an AlGaAs double heterostructure are differentially etched in a neutral solution of H2O2. The latter step is particularly useful in the fabrication of active devices because the resulting structure is self-masking, thereby facilitating the formation of electrical contacts.

Abstract translation: 制造介质光波导的方法包括以下步骤：（1）优选地通过液相外延或分子束外延从GaAs-AlGaAs系统制造单或双异质结构; （2）通过阳极氧化在H 2 O 2中在异质结构的顶表面上形成天然氧化物层; （3）除去氧化物层的一部分以形成掩模，从而在光传播的方向上限定波导形状; 和（4）通过在Br 2 -CH 3 OH中以缓慢的速率蚀刻形成具有光学平坦侧壁的台面状结构。 在步骤（4）之后，可以遵循导致结构不同的波导的两种替代技术。 在一种技术中，在台面上外延生长AlGaAs层以形成二维波导。 在另一种技术中，AlHAs双异质结构的有源区的边缘在H 2 O 2的中性溶液中进行差分蚀刻。 后一步骤在制造有源器件中特别有用，因为所得到的结构是自掩蔽的，从而有助于电接触的形成。

公开(公告)号：US3484312A

公开(公告)日：1969-12-16

申请号：US3484312D

申请日：1966-12-28

Applicant: BELL TELEPHONE LABOR INC

Inventor： ERMANIS FELIX ,  SCHWARTZ BERTRAM

IPC: H01L21/00 ,  H01L21/24 ,  H01L23/58 ,  H01L29/207 ,  H01L7/46

CPC classification number: H01L23/58 ,  H01L21/00 ,  H01L21/24 ,  H01L29/207 ,  H01L2924/0002 ,  Y10S148/018 ,  Y10S148/02 ,  H01L2924/00

公开(公告)号：US3894919A

公开(公告)日：1975-07-15

申请号：US46842474

申请日：1974-05-09

Applicant: BELL TELEPHONE LABOR INC

Inventor： SCHWARTZ BERTRAM ,  SPITZER STUART MARSHALL ,  WEIGLE GREGORY DYETT

IPC: H01L21/316 ,  H01L33/30 ,  H01L33/38 ,  H01L33/40 ,  H01L33/44 ,  C25D11/00 ,  C25D5/02

CPC classification number: H01L33/44 ,  H01L21/31687 ,  H01L33/30 ,  H01L33/387 ,  H01L33/40

Abstract: A method is described which permits electrolytic oxidation of semiconductor samples with contact metallization in place. An anodizable metal such as Al, Ni, Ta, Ti, Zn or alloys including such metal is deposited over the contacts. During electrolytic oxidation, the oxide formed over the metal closes off shunting paths which would normally exist through the contacts and thereby permits a native oxide to grow into the exposed surface of the semiconductor. The oxide formed over the metal can be easily cracked under mechanical pressure to permit electrical connection to the contacts in the final device.

Abstract translation: 描述了允许在接触金属化就位的半导体样品的电解氧化的方法。 诸如Al，Ni，Ta，Ti，Zn的阳极化金属或包括这种金属的合金沉积在触点上。 在电解氧化期间，形成在金属上的氧化物封闭通常通过触点存在的分流路径，从而允许天然氧化物生长到半导体的暴露表面。 形成在金属上的氧化物可以在机械压力下容易地破裂，以允许电连接到最终装置中的触点。

公开(公告)号：US3890215A

公开(公告)日：1975-06-17

申请号：US44066474

申请日：1974-02-08

Applicant: BELL TELEPHONE LABOR INC

Inventor： DILORENZO JAMES VINCENT ,  NIEHAUS WILLIAM CHARLES ,  RODE DANIEL LEON ,  SCHWARTZ BERTRAM

IPC: H01L21/3063 ,  H01L21/316 ,  H01L29/00 ,  B23P1/00 ,  H01L7/00

CPC classification number: H01L21/31679 ,  H01L21/02241 ,  H01L21/02258 ,  H01L21/3063 ,  H01L21/30635 ,  H01L29/00 ,  Y10S438/977

Abstract: A method for precisely tailoring the thickness of a layer of semiconductor material in a structure comprising regions of varying doping concentrations in order to achieve desired uniform electrical properties. The method involves, generally, electrolytically thinning the layer to remove the semiconductor material until a desired field distribution in the structure is reached. In one embodiment, an FET with an epitaxial layer on a semi-insulating substrate is manufactured by successively oxidizing the epitaxial layer and dissolving the oxide until the depletion region resulting from the applied potential extends into the semi-insulating substrate and oxide growth stops. This results in a uniform pinch-off condition along the layer regardless of the original non-uniformity in the epitaxial layer. In a further embodiment, the epitaxial layer in an IMPATT structure is thinned by successive oxidation and dissolution until the voltage dropped across the semiconductor is equal to the applied potential and again oxide growth stops. This procedure results in a desired uniform breakdown voltage for the wafer.

Abstract translation: 一种用于在包括改变掺杂浓度的区域的结构中精确地定制半导体材料层的厚度的方法，以便实现期望的均匀电性能。 通常，该方法通常电解稀薄该层以去除半导体材料，直到达到结构中的期望的场分布。 在一个实施例中，在半绝缘衬底上具有外延层的FET通过连续地氧化外延层并溶解氧化物来制造，直到由所施加的电势产生的耗尽区延伸到半绝缘衬底中并且氧化物生长停止。 这导致沿着该层的均匀夹断条件，而不管外延层中的原始不均匀性如何。 在另一个实施方案中，通过连续的氧化和溶解使IMPATT结构中的外延层变薄，直到跨过半导体的电压下降等于所施加的电势，并且再次氧化物生长停止。 该过程导致晶片所需的均匀击穿电压。