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Let's cut to the chase. I've been researching through numerous, reliable and unreliable, resources. According to the CRT official site and wiki, the first cathode ray tube (CRT) was invented by Carl Ferdinand Braun, year 1897. Yet undeniable proofs of CRTs being used in experiments in 1860s have been collected.
So this leaves the question unanswered. Noting that one of the fundamental progresses in chemistry (discovery of electron) is based on this useful tube, I will be thankful to anyone willing to share some info.

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Invention of CRT

In the year 1855, German inventor Heinrich Geissler developed mercury pump which is later modified by Sir William Crookes who became the first to produce cathode rays.

Figure 1: Geissler's Vaccum tubes(1862)

Since, then vacuum tubes are being used to study cathode rays, Braun's tube was actually an improvement to the these.

Otherwise, all of them have used some kind of Vacuum tube which produces cathode rays.

  • In 1858 Julius Plücker showed that cathode rays bend under the influence of a magnet.
  • In 1865 H. Sprengel improves the Geissler vacuum pump.
  • In 1869 J.W. Hittorf establishes that "rays" from the cathode travel in straight lines.
  • In 1871 C.F. Varley is first to publish suggestion that cathode rays are composed of particles.[Fig 2]
  • In 1874 George Johnstone Stoney estimates the charge of the then unknown electron.
  • In 1876 Eugen Goldstein introduces the term cathode ray to describe the light emitted.
  • In 1881 Herman Ludwig von Helmholtz suggested the idea that there is a smallest unit of electricity.
  • In 1890 Arthur Schuster calculates the ratio of charge to mass of the particles making up cathode rays (today known as electrons) by measuring the magnetic deflection of cathode rays.
  • In 1894 J.J. Thomson announces that he has found that the velocity of cathode rays is much lower than that of light.

Source:

  1. http://www.chemteam.info/AtomicStructure/Disc-of-Electron-History.html
  2. http://www.chemteam.info/AtomicStructure/Disc-of-Electron-Intro.html

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Figure 2: First published paper on cathode rays.

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